Weakly Coordinating Anions and Lewis Superacidity
Inaugural-Dissertation
Zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften
(Dr rer nat)
von der Fakultaumlt fuumlr Chemie Pharmazie und Geowissenschaften
an der Albert-Ludwigs-Universitaumlt zu Freiburg
Promotionsausschuss Prof Dr R Schubert
Referent Prof Dr I Krossing
Koreferent Prof Dr C Janiak
Drittpruumlfer Prof Dr P Graumlber
Datum der Kollegialpruumlfung 06032008
vorgelegt von
Dipl-Chem Lutz O Muumlller
aus Marl Nordrhein-Westfalen
Januar 2008
Die vorliegende Arbeit entstand in der Zeit von Februar 2004 bis Januar 2008 am Institut fuumlr
Anorganische und Analytische Chemie der Universitaumlt Karlsruhe (TH) am Institut des
Sciences et Ingeacutenierie Chimiques der Eidgenoumlssischen Technischen Hochschule Lausanne
(ETH) und am Institut fuumlr Anorganische und Analytische Chemie der Albert-Ludwigs-
Universitaumlt zu Freiburg i Br unter der Leitung von Prof Dr Ingo Krossing
Meinen Eltern gewidmet
An dieser Stelle moumlchte ich all denjenigen herzlich danken die zum Gelingen dieser Arbeit
beigetragen haben
meinem Doktorvater Prof Dr Ingo Krossing fuumlr die interessante Aufgabenstellung
seine Unterstuumltzung und Betreuung sowie die wissenschaftliche Diskussion der
Ergebnisse
den Mitgliedern der Pruumlfungskommission Prof Dr Christoph Janiak und
Prof Dr Peter Graumlber
meinen aktuellen und ehemaligen AK- und Laborkollegen Dr Andreas Reisinger
Boumahdi Benkmil Dr Carsten Knapp Dr Daniel Himmel Fadime Bitguumll
Dr Gunther Steinfeld Dr Gustavo Santiso Dr Ines Raabe Dr Jens Hartig
Dr John Slattery Katrin Wagner Kristin Guttsche Lucia Alvarez Dr Marcin Gonsior
Nils Trapp Petra Klose Philipp Eiden Şafak Bulut Tobias Koumlchner Ulrich Preiss und
Dr Werner Deck fuumlr die angenehme Arbeitsatmosphaumlre
insbesondere meinen Laborkollegen Dr Gustavo Santiso Philipp Eiden Tobias
Koumlchner und Ulrich Preiss fuumlr die Hilfeleistung bei vielen wissenschaftlichen Fragen
Tobias Koumlchner fuumlr das sorgfaumlltige Korrekturlesen der vorliegenden Arbeit
Vera Bruksch Monika Kayas Gerda Probst Sylvia Soldner und
Christina Zamanos Epremian fuumlr die notwendigen Sekretariatsarbeiten
Dr Rosario Scopelliti Dr Gustavo Santiso und Dr Gunther Steinfeld fuumlr die Hilfe bei der
Durchfuumlhrung und Auswertung von Roumlntgenstrukturanalysen
Helga Berberich Dr Eberhardt Matern Sibylle Schneider und Volker Brecht fuumlr die
Aufnahme von zahlreichen NMR-Spektren
Fabrice Ribelet fuumlr die hilfreiche Einarbeitung am NMR-Geraumlt in Lausanne
der Firma Iolitec fuumlr die Bereitstellung einiger ionischer Fluumlssigkeiten
Julia Stauffer fuumlr ihre experimentellen Beitraumlge zur Chemie der Lewis Superaciditaumlt sowie
ihre freundschaftliche Unterstuumltzung
Kalam Keilhauer Peter Neuenschwander und Tim Oelsner fuumlr die Anfertigung und
Reparatur von Glasgeraumlten
den Mitarbeitern der feinmechanischen Werkstaumltten in Lausanne insbesondere
Renato Bregonzi Roger Ith Christian Roll und Markus Melder in Freiburg fuumlr die
Anfertigung und Reparatur von Geraumlten und Apparaturen
den Mitarbeitern der Chemikalienshops Gabi Kuhne Gladys Pache Giovanni Petrucci
Monika Voumllker und Friedbert Jerg fuumlr die Beschaffung von Chemikalien
meinen Eltern meinem Bruder und meiner Oma die mich waumlhrend meines
Studiums und der Promotionszeit immer unterstuumltzt haben
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
Die vorliegende Arbeit entstand in der Zeit von Februar 2004 bis Januar 2008 am Institut fuumlr
Anorganische und Analytische Chemie der Universitaumlt Karlsruhe (TH) am Institut des
Sciences et Ingeacutenierie Chimiques der Eidgenoumlssischen Technischen Hochschule Lausanne
(ETH) und am Institut fuumlr Anorganische und Analytische Chemie der Albert-Ludwigs-
Universitaumlt zu Freiburg i Br unter der Leitung von Prof Dr Ingo Krossing
Meinen Eltern gewidmet
An dieser Stelle moumlchte ich all denjenigen herzlich danken die zum Gelingen dieser Arbeit
beigetragen haben
meinem Doktorvater Prof Dr Ingo Krossing fuumlr die interessante Aufgabenstellung
seine Unterstuumltzung und Betreuung sowie die wissenschaftliche Diskussion der
Ergebnisse
den Mitgliedern der Pruumlfungskommission Prof Dr Christoph Janiak und
Prof Dr Peter Graumlber
meinen aktuellen und ehemaligen AK- und Laborkollegen Dr Andreas Reisinger
Boumahdi Benkmil Dr Carsten Knapp Dr Daniel Himmel Fadime Bitguumll
Dr Gunther Steinfeld Dr Gustavo Santiso Dr Ines Raabe Dr Jens Hartig
Dr John Slattery Katrin Wagner Kristin Guttsche Lucia Alvarez Dr Marcin Gonsior
Nils Trapp Petra Klose Philipp Eiden Şafak Bulut Tobias Koumlchner Ulrich Preiss und
Dr Werner Deck fuumlr die angenehme Arbeitsatmosphaumlre
insbesondere meinen Laborkollegen Dr Gustavo Santiso Philipp Eiden Tobias
Koumlchner und Ulrich Preiss fuumlr die Hilfeleistung bei vielen wissenschaftlichen Fragen
Tobias Koumlchner fuumlr das sorgfaumlltige Korrekturlesen der vorliegenden Arbeit
Vera Bruksch Monika Kayas Gerda Probst Sylvia Soldner und
Christina Zamanos Epremian fuumlr die notwendigen Sekretariatsarbeiten
Dr Rosario Scopelliti Dr Gustavo Santiso und Dr Gunther Steinfeld fuumlr die Hilfe bei der
Durchfuumlhrung und Auswertung von Roumlntgenstrukturanalysen
Helga Berberich Dr Eberhardt Matern Sibylle Schneider und Volker Brecht fuumlr die
Aufnahme von zahlreichen NMR-Spektren
Fabrice Ribelet fuumlr die hilfreiche Einarbeitung am NMR-Geraumlt in Lausanne
der Firma Iolitec fuumlr die Bereitstellung einiger ionischer Fluumlssigkeiten
Julia Stauffer fuumlr ihre experimentellen Beitraumlge zur Chemie der Lewis Superaciditaumlt sowie
ihre freundschaftliche Unterstuumltzung
Kalam Keilhauer Peter Neuenschwander und Tim Oelsner fuumlr die Anfertigung und
Reparatur von Glasgeraumlten
den Mitarbeitern der feinmechanischen Werkstaumltten in Lausanne insbesondere
Renato Bregonzi Roger Ith Christian Roll und Markus Melder in Freiburg fuumlr die
Anfertigung und Reparatur von Geraumlten und Apparaturen
den Mitarbeitern der Chemikalienshops Gabi Kuhne Gladys Pache Giovanni Petrucci
Monika Voumllker und Friedbert Jerg fuumlr die Beschaffung von Chemikalien
meinen Eltern meinem Bruder und meiner Oma die mich waumlhrend meines
Studiums und der Promotionszeit immer unterstuumltzt haben
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
Meinen Eltern gewidmet
An dieser Stelle moumlchte ich all denjenigen herzlich danken die zum Gelingen dieser Arbeit
beigetragen haben
meinem Doktorvater Prof Dr Ingo Krossing fuumlr die interessante Aufgabenstellung
seine Unterstuumltzung und Betreuung sowie die wissenschaftliche Diskussion der
Ergebnisse
den Mitgliedern der Pruumlfungskommission Prof Dr Christoph Janiak und
Prof Dr Peter Graumlber
meinen aktuellen und ehemaligen AK- und Laborkollegen Dr Andreas Reisinger
Boumahdi Benkmil Dr Carsten Knapp Dr Daniel Himmel Fadime Bitguumll
Dr Gunther Steinfeld Dr Gustavo Santiso Dr Ines Raabe Dr Jens Hartig
Dr John Slattery Katrin Wagner Kristin Guttsche Lucia Alvarez Dr Marcin Gonsior
Nils Trapp Petra Klose Philipp Eiden Şafak Bulut Tobias Koumlchner Ulrich Preiss und
Dr Werner Deck fuumlr die angenehme Arbeitsatmosphaumlre
insbesondere meinen Laborkollegen Dr Gustavo Santiso Philipp Eiden Tobias
Koumlchner und Ulrich Preiss fuumlr die Hilfeleistung bei vielen wissenschaftlichen Fragen
Tobias Koumlchner fuumlr das sorgfaumlltige Korrekturlesen der vorliegenden Arbeit
Vera Bruksch Monika Kayas Gerda Probst Sylvia Soldner und
Christina Zamanos Epremian fuumlr die notwendigen Sekretariatsarbeiten
Dr Rosario Scopelliti Dr Gustavo Santiso und Dr Gunther Steinfeld fuumlr die Hilfe bei der
Durchfuumlhrung und Auswertung von Roumlntgenstrukturanalysen
Helga Berberich Dr Eberhardt Matern Sibylle Schneider und Volker Brecht fuumlr die
Aufnahme von zahlreichen NMR-Spektren
Fabrice Ribelet fuumlr die hilfreiche Einarbeitung am NMR-Geraumlt in Lausanne
der Firma Iolitec fuumlr die Bereitstellung einiger ionischer Fluumlssigkeiten
Julia Stauffer fuumlr ihre experimentellen Beitraumlge zur Chemie der Lewis Superaciditaumlt sowie
ihre freundschaftliche Unterstuumltzung
Kalam Keilhauer Peter Neuenschwander und Tim Oelsner fuumlr die Anfertigung und
Reparatur von Glasgeraumlten
den Mitarbeitern der feinmechanischen Werkstaumltten in Lausanne insbesondere
Renato Bregonzi Roger Ith Christian Roll und Markus Melder in Freiburg fuumlr die
Anfertigung und Reparatur von Geraumlten und Apparaturen
den Mitarbeitern der Chemikalienshops Gabi Kuhne Gladys Pache Giovanni Petrucci
Monika Voumllker und Friedbert Jerg fuumlr die Beschaffung von Chemikalien
meinen Eltern meinem Bruder und meiner Oma die mich waumlhrend meines
Studiums und der Promotionszeit immer unterstuumltzt haben
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
An dieser Stelle moumlchte ich all denjenigen herzlich danken die zum Gelingen dieser Arbeit
beigetragen haben
meinem Doktorvater Prof Dr Ingo Krossing fuumlr die interessante Aufgabenstellung
seine Unterstuumltzung und Betreuung sowie die wissenschaftliche Diskussion der
Ergebnisse
den Mitgliedern der Pruumlfungskommission Prof Dr Christoph Janiak und
Prof Dr Peter Graumlber
meinen aktuellen und ehemaligen AK- und Laborkollegen Dr Andreas Reisinger
Boumahdi Benkmil Dr Carsten Knapp Dr Daniel Himmel Fadime Bitguumll
Dr Gunther Steinfeld Dr Gustavo Santiso Dr Ines Raabe Dr Jens Hartig
Dr John Slattery Katrin Wagner Kristin Guttsche Lucia Alvarez Dr Marcin Gonsior
Nils Trapp Petra Klose Philipp Eiden Şafak Bulut Tobias Koumlchner Ulrich Preiss und
Dr Werner Deck fuumlr die angenehme Arbeitsatmosphaumlre
insbesondere meinen Laborkollegen Dr Gustavo Santiso Philipp Eiden Tobias
Koumlchner und Ulrich Preiss fuumlr die Hilfeleistung bei vielen wissenschaftlichen Fragen
Tobias Koumlchner fuumlr das sorgfaumlltige Korrekturlesen der vorliegenden Arbeit
Vera Bruksch Monika Kayas Gerda Probst Sylvia Soldner und
Christina Zamanos Epremian fuumlr die notwendigen Sekretariatsarbeiten
Dr Rosario Scopelliti Dr Gustavo Santiso und Dr Gunther Steinfeld fuumlr die Hilfe bei der
Durchfuumlhrung und Auswertung von Roumlntgenstrukturanalysen
Helga Berberich Dr Eberhardt Matern Sibylle Schneider und Volker Brecht fuumlr die
Aufnahme von zahlreichen NMR-Spektren
Fabrice Ribelet fuumlr die hilfreiche Einarbeitung am NMR-Geraumlt in Lausanne
der Firma Iolitec fuumlr die Bereitstellung einiger ionischer Fluumlssigkeiten
Julia Stauffer fuumlr ihre experimentellen Beitraumlge zur Chemie der Lewis Superaciditaumlt sowie
ihre freundschaftliche Unterstuumltzung
Kalam Keilhauer Peter Neuenschwander und Tim Oelsner fuumlr die Anfertigung und
Reparatur von Glasgeraumlten
den Mitarbeitern der feinmechanischen Werkstaumltten in Lausanne insbesondere
Renato Bregonzi Roger Ith Christian Roll und Markus Melder in Freiburg fuumlr die
Anfertigung und Reparatur von Geraumlten und Apparaturen
den Mitarbeitern der Chemikalienshops Gabi Kuhne Gladys Pache Giovanni Petrucci
Monika Voumllker und Friedbert Jerg fuumlr die Beschaffung von Chemikalien
meinen Eltern meinem Bruder und meiner Oma die mich waumlhrend meines
Studiums und der Promotionszeit immer unterstuumltzt haben
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
Kalam Keilhauer Peter Neuenschwander und Tim Oelsner fuumlr die Anfertigung und
Reparatur von Glasgeraumlten
den Mitarbeitern der feinmechanischen Werkstaumltten in Lausanne insbesondere
Renato Bregonzi Roger Ith Christian Roll und Markus Melder in Freiburg fuumlr die
Anfertigung und Reparatur von Geraumlten und Apparaturen
den Mitarbeitern der Chemikalienshops Gabi Kuhne Gladys Pache Giovanni Petrucci
Monika Voumllker und Friedbert Jerg fuumlr die Beschaffung von Chemikalien
meinen Eltern meinem Bruder und meiner Oma die mich waumlhrend meines
Studiums und der Promotionszeit immer unterstuumltzt haben
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
List of Abbreviations -1- Abbreviation Meaning 12ndashF2Ph 12-difluorobenzene a unit cell dimension au arbitrary unit ArF fluorinated aryl ligand b unit cell dimension br broad Bu butyl C4H10 c unit cell dimension d distance dublet DFT density functional theory eq equivalent Et ethyl ndashCH2ndashCH3 FIA Fluoride Ion Affinity Gdeg standard Gibbs energy GOOF goodness of fit Hdeg standard enthalpy ie id est for instance IR infra red J coupling constant L ligand m multiplett m mw ms medium medium weak medium
strong Me methyl ndashCH3 NMR nuclear magnetic resonance Ph phenyl ndashC6H5 q quartett RF C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2
and others r t room temperature s strong singlet sep septet sh shoulder t triplet tBu 22 Dimethyl-ethyl ndashC(CH3)3 THF tetrahydrofurane C4H8O tol toluene V volume v vw vs very very weak very strong vs vide supra see above w weak
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten
List of Abbreviations -2- Abbreviation Meaning WCA weakly coordinating anion Z number of formula per unit cell ZPE zero point energy α unit cell angle β unit cell angle γ unit cell angle εr dielectric constant λ wavelength micro absorption coefficient ν wave number ρ density
TABLE OF CONTENTS
Abstract Zusammenfassung 1
A Introduction
Weakly Coordinating Anions (WCAs) ndash Definition and Properties 3
Aim of This Work 12
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu mesitylene) 17
B1 Lithium alkoxides as precursors for WCAs 17
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash 19
B12 Crystal Structures 21
B13 DFT calculations 23
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol RFOH and
attempts to usem them as precursors for new WCAs 24
B21 Syntheses and Crystal Structures 25
B211 Synthesis of LiMesOEt2 25
B212 Synthesis of [LiOC(CF3)2Mes]4 25
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 27
B214 Synthesis of HOC(CF3)2Mes 29
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] 31
B3 Conclusion 33
C A Highly Hexane Soluble Lithium Salt and other Starting Materials of the
Fluorinated Weakly Coordinating Anion [Al(OC(CF3)2(CH2SiMe3))4]ndash 35
C1 Syntheses 36
C11 Attempted further synthesis of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash 39
C2 Crystal Structure 39
C3 Conclusion 42
D A Simple Access to the non-oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) 44
D1 Conclusion 52
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3) 55
E1 Syntheses 56
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3 56
E111 Synthesis of Me3SindashFndashAl(ORF)3 56
E112 Fluoride ion abstraction from [BF4]ndash-salts 57
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 58
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 59
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash 60
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 60
E117 Representative NMR-Data of the Fluoroaluminates 61
E2 Crystal Structures 62
E21 Me3SindashFndashAl(ORF)3 63
E22 [Ag(arene)3]+[FAl(ORF)3]ndash 63
E23 [Ph3C]+[FAl(ORF)3]ndash 66
E231 Comparison of the [FAlORF)3]ndash Structures 67
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 68
E233 Bonding around Si in the ion-like compound 70
E24 Structures with AlndashFndashAl bridges 71
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 72
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 72
E2421 Comparison of the structural parameters of the fluoride bridged anions 74
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of
[Ag(arene)3]+-salts of [(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash74
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts76
E4 Conclusion 78
F Summary 82
G Experimental Section 89
G1 General Experimental Techniques 89
G11 General Procedures and Starting Materials 89
G12 NMR Spectroscopy 89
G13 IR and Raman Spectroscopy 90
G14 X-Ray Diffraction and Crystal Structure Determination 90
G15 Syntheses and Spectroscopic Analyses 92
G151 Preparation of [Li(OC(H)(CF3)2]42Et2O 92
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 93
G153 Preparation of (CF3)2(H)COMg2Et2O 94
G154 Preparation of MesndashLiOEt2 95
G155 Preparation of [LiOC(CF3)2Mes]4 97
G156 Preparation of HOC(CF3)2Mes 98
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 99
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 100
G159 Preparation of LiOC(CF3)2CH2SiMe3 101
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash 102
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash in one pot 103
G1512 NMR scale reactions 104
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash 105
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 106
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 108
G1516 First Preparation of Me3SindashFndashAl(ORF)3 109
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 110
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash 111
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash 112
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash 113
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash 114
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash 115
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash 116
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash 117
H Theoretical Section 119
H1 Frequency Calculations Thermal Corrections and Solvation Energies 119
H2 Lattice Energy Calculations 120
I Appendix 122
I1 Numbering of the compounds 122
J Appendix 123
J1 Appendix to Chapter C 123
J2 Appendix to Chapter D 125
J3 Appendix to Chapter E 129
K Computational data of all calculated species 133
L Crystal Structure Tables 139
M Atomic Coordinates 143
N Publications 167
O Lectures Conferences and Posters 169
1
Abstract Zusammenfassung
Abstract
During the last decades weakly coordinating anions (WCAs) became a field of great interest both in basic and applied chemistry Compared to ldquonormalrdquo common classical anions they have a lot of unique and unusual properties ie feature high solubility in low dielectric media (like CH2Cl2 or toluene) lead to ldquopseudo gas phase conditionsrdquo in condensed phases and are able to stabilize unusual cationic states as well as weakly bound and low charged cationic complexes In more applied chemistry they promote catalytic activity are the counterions for Ionic Liquids and many more The objectives of this thesis were the investigations of new WCAs and a thereof derived Lewis acid
To synthesize bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = tBu mesityl or CH2SiMe3 residues) the syntheses of the corresponding fluorinated lithium alkoxides LiORF or alcohols HORF were explored These alkoxidesalcohols were used as building blocks and precursors for novel weakly coordinating anions In this way the novel hexane soluble lithium alkoxide Li[Al(OC(CF3)2CH2SiMe3)4] could be synthesized which should be an excellent candidate for Li ion catalysis and for the coordination chemistry of Li+ with weak ligands
The basis of our [Al(ORF)4]ndash-WCA (RF = C(CF3)3) is the strong Lewis acid Al(ORF)3 In addition to the complete characterization of Al(ORF)3 the acid and its strength was compared to already known classical Lewis acids A reliable measure for the Lewis acidity of A(g) with the respect to the fluoride ion Fndash
(g) is the fluoride ion affinity (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
The enthalpy ∆H corresponds the negative of the FIA and the higher the FIA value the stronger is the Lewis acid Analogously to Broslashnstedt Superacids (those stronger than 100 H2SO4) the term Lewis Superacids was defined within this work
Molecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in the gas phase (FIA = ndash489 kJ molndash1) are Lewis Superacids
Due to the strong acidity of pure Al(ORF)3 (FIA = ndash537 kJ molndash1) the decomposition via internal CndashF bond activation to the Lewis acidic aluminium atom made it difficult to isolate it as such To overcome this problem the stabilized fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) has been developed to provide an easily accessible room temperature stable reagent With this compound the Lewis Superacidity was further experimentally supported by the reactions with suitable sources of [SbF6]ndash and [PF6]ndash eg the Ionic Liquids [BMIM]+[SbF6]ndash and [BMIM]+[PF6]ndash (BMIM = buthylmethylimidazolium) performed and proceeded successfully with fluoride abstraction from [SbF6]ndash Hence the Lewis Superacid PhndashFrarrAl(ORF)3 may widely be used in all applications that need high and hard Lewis acidity
Using the Lewis Superacid Al(ORF)3 a novel WCA type has been introduced in this thesis the robust [FAl(ORF)3]ndash-anion which by forming an ion-like compound is stable even in the presence of fierce electrophiles like [Me3Si]+ Moreover a simple and straight-forward access to many simple [FAl(ORF)3]ndash-salts has been developed and opened the straight one step access to several salts of the already earlier investigated [(RFO)3AlndashFndashAl(ORF)3]ndash-anion (RF = C(CF3)3)
Most of the subjects treated experimentally within this thesis have been accompanied and proven by quantum-chemical calculations
Keywords weakly coordinating anions (WCAs) lithium alkoxides lithium alkoxy aluminates Lewis Superacidity FIA quantum chemical calculations
2
Zusammenfassung
Im Laufe der letzten Jahrzehnte hat sich die Chemie der schwach koordinierenden Anionen (WCAs weakly coordinating anions) zu einem Gebiet entwickelt das sowohl in der Grundlagenforschung als auch in der angewandten Chemie von groszligem Interesse ist Im Vergleich zu den bdquonormalenldquo klassischen Anionen weisen einige WCAs einzigartige und ungewoumlhnliche Eigenschaften auf Sie sind beispielsweise gut in unpolaren Loumlsungsmitteln wie CH2Cl2 oder Toluol loumlslich fuumlhren zu bdquoPseudo-Gasphasen-Bedingungenldquo in kondensierter Phase und sind in der Lage ungewoumlhnliche Kationenzustaumlnde sowie schwach gebundene und niedrig geladene kationische Komplexe zu stabilisieren In der anwendungsbezogeneren Chemie verstaumlrken sie die katalytische Aktivitaumlt und dienen als Gegenionen fuumlr Ionische Fluumlssigkeiten und vieles mehr Die Ziele dieser Arbeit waren die Erforschung neuartiger WCAs sowie einer daraus abgeleiteten Lewis Saumlure
Um sperrige schwach koordinierende Anionen des Typs [Al(ORF)4]ndash (RF = C(R)(CF3)2 mit R = tBu Mesityl oder CH2SiMe3 Resten) zu synthetisieren wurden Synthesewege zu den korrespondierenden Lithiumalkoxiden LiORF oder Alkoholen HORF erarbeitet Diese AlkoxideAlkohole wurden als Bausteine und Ausgangsverbindungen fuumlr neuartige WCAs genutzt In dieser Art und Weise konnte die neuartige hexan loumlsliche Lithiumalkoxidverbindung Li[Al(OC(CF3)2CH2SiMe3)4] synthetisiert werden die ein exzellenter Kandidat fuumlr Lithium Ionen Katalyse und Koordinationschemie von Li+ mit schwachen Liganden sein sollte
Die Basis bildende Komponente des [Al(ORF)4]ndash-WCA (RF = C(CF3)3) ist die starke Lewis Saumlure Al(ORF)3 Neben der vollstaumlndigen Charakterisierung von Al(ORF)3 wurde die Saumlure und deren Staumlrke mit bekannten klassischen Lewis Saumluren verglichen Eine bewaumlhrte Meszliggroumlszlige fuumlr die Lewis Aziditaumlt von A(g) in Bezug auf das Fluoridion Fndash
(g) ist die Fluoridionenaffinitaumlt (FIA)
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+
Die Enthalpie ∆H korrespondiert mit dem negativen Wert der FIA Je groumlszliger die FIA desto staumlrker die Lewis Saumlure Analog zu den Broslashnstedt Supersaumluren (diejenigen die staumlrker als 100 H2SO4 sind) wurde in dieser Arbeit der Begriff Lewis Supersaumlure definiert
Molekulare Lewis Saumluren die staumlrker als monomeres SbF5 in der Gasphase sind (eine houmlhere FIA als ndash489 kJ molndash1 haben) sind Lewis Supersaumluren
Aufgrund der hohen Aziditaumlt und der leichten Zersetzbarkeit von reinem Al(ORF)3 (FIA = ndash537 kJ molndash1) durch interne CndashF Bindungsaktivierung zum Lewis aciden Aluminiumatom war es schwierig die Verbindung als solche zu isolieren Um dieser Problematik entgegenzuwirken wurde der stabilisierte Fluorbenzol-Addukt-Komplex PhndashFrarrAl(ORF)3 (FIA = ndash505 kJ molndash1) entwickelt der eine bei Raumtemperatur stabile Verbindung darstellt Des Weiteren konnte mit dieser Verbindung die Lewis Superaziditaumlt experimentell belegt werden Dazu wurden die Ionischen Fluumlssigkeiten [BMIM]+[SbF6]ndash und [BMIM]+[PF6]ndash (BMIM = Butylmethylimidazolium) welche als geeignete Quellen fuumlr [SbF6]ndash und [PF6]ndash dienten mit der Supersaumlure umgesetzt Die erfolgreiche FndashndashAbstraktion von [SbF6]ndash verdeutlicht die Staumlrke der Saumlure Demzufolge kann die Lewis Supersaumlure PhndashFrarrAl(ORF)3 fuumlr Anwendungen eingesetzt werden in denen starke und harte Lewis Aziditaumlt benoumltigt wird
Durch Verwendung dieser Lewis-Saumlure konnte ein neuartiger WCA-Typ in dieser Arbeit erhalten werden naumlmlich das robuste [FAl(ORF)3]ndash-Anion welches unter Bildung einer ionenartigen Verbindung sogar stabil in Gegenwart so starker Elektrophile wie zB dem [Me3Si]+ Kation ist Daruumlber hinaus ist ein einfacher direkter Zugang zu vielen [FAl(ORF)3]ndash-Salzen entwickelt worden damit konnte die direkte Einstufensynthese zu verschiedenen Salzen des bereits fruumlher synthetisierten Anions [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) eroumlffnet werden
Die meisten experimentellen Ergebnisse in dieser Arbeit wurden durch quantenmechanische Rechnungen bestaumltigt und ergaumlnzt
Schlagworte Schwach koordinierende Anionen Lithiumalkoxide Lithiumalkoxyaluminate Lewis-Superaciditaumlt FIA quantenmechanische Rechnungen
3
A Introduction
Weakly coordinating anions (WCAs) ndash Definition and Properties
About three decades ago the term ldquonon-coordinating anionrdquo was optimistically used when a
small anion ie halide Xndash was replaced by a bigger complex anion such as BF4ndash CF3SO3
ndash
ClO4ndash AlX4
ndash or MF6ndash (X = F-I M = P As Sb etc) However with the advances in X-ray
structure determination it became obvious that also these anions coordinate to suitable
counterions[1] In the last decade the term ldquoweakly coordinating anionsrdquo (WCAs) was created
which more accurately describes the interaction between anion and cation and already
underlines the potential of such complexes to serve as precursor of a ldquonon-coordinatingrdquo
cation Owing to the importance of such WCAs both in fundamental[2 3] and applied[4]
chemistry many efforts were undertaken to finally reach the ultimate goal of a truly ldquonon-
coordinatingrdquo anion However the existence of an anion that has no capacity for coordination
is impossible[5 6] Each anion in solution competes with the solvent for coordination to the
cation Thus an anion can in certain systems be classed as ldquonon-coordinatingrdquo when it
shows a weaker coordination than the solvent[5] Since SH Straussrsquo article on WCAs[3] has
been widely cited plenty of new so-called ldquosuperweak anionsrdquo[7] have been developed Some
of the most common examples of the new generation of large and chemically robust WCAs
are eg [B(C6F5)4]ndash[8] [Sb(OTeF5)6]ndash[9 10] [CB11Me6X6]ndash[2 11] or [Al(ORF)4]ndash[12 13]
For a basic approach to develop weakly coordinating anions it is essential that the negative
charge ndash apart from some special cases only singly charged anions are considered ndash should be
distributed and delocalized over a large number of ligand atoms to minimize the electrostatic
cation-anion interaction and approximate cationic states in condensed phase In addition the
peripherical atoms should be fluorine or hydrogen atoms and not oxygen or chlorine atoms
which coordinate more strongly Using bulky F-containing substituents as a strongly electron
withdrawing group a hardly polarizable periphery is created With respect to this bulkiness
4
the basic sites like the O-atoms in the [Al(ORF)4]ndash-anion (RF = (per-)fluorinated bulky rest)
may be hidden Therefore the accessibility for electrophilic attacks can be consequently
reduced which protects the anion from ligand abstraction the moderately strong coordinating
anions such as [BF4]ndash [PF6]ndash and [SbF6]ndash are unstable towards those electrophilic attacks and
loose Fndash Thus WCAs allow the stabilization of strongly acidic gas phase species highly
electrophilic metal and non metal cations or weakly bound Lewis acid-base complexes of
metal cations[2-4 14-17] Examples of this kind of unusual and fundamentally important cations
include [Au(Xe)4]2+[18] [Xe2]+[19] [Xe4]+[20] [HC60]+[21] [Mes3Si]+[22] [Ag(L)2]+ (L = CO[23]
C2H2[24 25] C2H4
[24-26] P4[27 28] S8
[29] P4S3[30]) [P5X2]+ (X = Br I)[17 31] [CX3]+ (X = Cl Br
I)[32-34] [N5]+[35] and many more Since WCAs are frequently used to stabilize very reactive
electrophiles they should only be chemically inert prepared to prevent from decomposition
Apart from being useful in fundamental chemistry WCAs are important for homogenous
catalysis[36-38] polymerizations[4 39-46] electrochemistry[47-54] ionic liquids[55-57]
photolithography[58-63] lithium ion batteries or super capacitors[64-67] However a variety of
different WCAs has been established in the literature especially throughout the last two
decades In the following section the most popular ones from literature are compared to those
used in our group The properties and applied qualities from each species differ since factors
such as coordination ability chemical robustness cost of synthesis and preparative
complexity vary with each anion Apart from the classical [BF4]ndash- and [MF6]ndash-anions larger
anions of the type [MnF5n+1]ndash (M = As Sb n = 2-4) are known in superacid solution (FigA-
1)
5
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
[Sb2F11]ndash [Sb3F16]ndash
[Sb4F21]ndash
Fig A-1 Structures of selected multinuclear fluorometallate-based WCAs as ball-and-stick models
A large problem associated with all fluorometallates is that mixtures with varying n-values
exit in solution which provides the free Lewis acid MF5 that may serve as an oxidizing agent
and thus may lead to unwanted side reactions Exchanging the fluorine atoms in a [BF4]ndash-
anion leads to polyfluorinated tetraaryl- or tetraalkylborates [B(RF)4]ndash (ie RF = ndashCF3[68] ndash
C6F5[8] or ndashC6H3-35-(CF3)2
[69 70]) (Fig A-2)
[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash[B(CF3)4]ndash [B(C6F5)4]ndash [B(C6H3-35-(CF3)2)4]ndash
Fig A-2 Structures of selected borate-based anions as ball-and-stick models
6
Salts of the latter two anions are commercially available and thus promote their use in many
applications eg homogenous catalysis[36] The systematic exchange of an F-atom in
[B(C6F5)4]ndash against other fluorinated and alkoxy rests gave several new anions of the type
[B(C6F4R)4]ndash eg R = CF3[71] Si(iPr)3
[72 73] or SiMe2tBu[72 73] Another anion modification
gave the reaction of two equivivalents of B(C6F5)3 with strong and hard nucleophiles Xndash such
as [CN]ndash[74 75] [C3N2H3]ndash[76] [NH2]ndash[77] etc The resulting dimeric [(F5C6)3B(micro-X)B(C6F5)3]ndash
borates are simple to prepare and may even stabilize strong electrophilic cations such as
H(OEt2)2+[77] (Fig A-3)
[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash[(C6F5)3B(micro-CN)B(C6F5)3]ndash [(C6F5)3B(micro-C3N2H3)B(C6F5)3]ndash
Fig A-3 Structures of selected bridged borate based anions as ball and stick models
In general borate based anions are commercially very interesting and gave very good results
as counterions for catalysts[69 70 74] However some borate anions (eg [CB11(CF3)12]ndash[78] see
also below) tend to explode and the phenyl rings might coordinate to metal cations which
lead to anion decomposition
Similarly to such alkyl borates the substitution of the fluorine atoms in [BF4]ndash and [MF6]ndash
anions by larger teflate groups OTeF5 led to the large and robust [B(OTeF5)4]ndash[79]- and
[M(OTeF5)6]ndash-anions (M = As[80] Sb[9 10 80] Bi[80] Nb[9 81]) (Fig A-4) These anions are a
structural altenative to the fluorinated alkyl- or arylborates
7
[B(OTeF5)4]ndash [As(OTeF5)6]ndash[B(OTeF5)4]ndash [As(OTeF5)6]ndash
Fig A-4 Structures of the teflate bases anions [B(OTeF5)4]ndash (left) and [As(OTeF5)6]ndash (right) as ball-and-stick
models
However all teflate based WCAs require the strict exclusion of moisture and decompose
rapidly in the presence of traces of moisture especially in glass equipment (SiO2) though
they might liberate HF very easily and initiate auto catalytic decomposition (Eq A-1)
[OTeF5]ndash + H2O HF + [OTeF4(OH)]ndash
4HF + SiO2 SiF4 + 2H2O (Eq A-1)
Alternatively another class of boron containing WCAs has been established the univalent
polyhedral carborates [CB9H10]ndash[82] or [CB11H12]ndash[83] Although the exohedral BndashH bonds in
these anions are very stable and only weakly coordinating oxidation may occur easily
Therefore a novel type of halogenated and (trifluoro)methylated carboranes [CB11XnH12-n]ndash (n
= 0-12 X = F Cl Br I CH3 CF3)[84-88] has been prepared by substituting successively the H-
atoms (Fig A-5)
8
[1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash [1-EtCB11F21]ndash[B11H6Cl6]ndash[HCB11Me5Cl6]ndash
Fig A-5 Structures of selected carboranates as ball-and-stick models
Although the carborane anions are the chemically most robust WCAs they are not widely
used due to enormous synthetic efforts and high costs
Obviously the development of new easy accessible and chemically robust WCAs without the
former mentioned disadvantages has been necessary Anions of the type [M(OArF)n]ndash (ArF =
poly-per-fluorinated ligand cf Fig A-6) satisfy the criteria of these requirements and are a
structural alternative to the fluorinated alkyl- or arylborates In principle they are built from a
central Lewis acidic atom MIII or MV (M = Al Nb Ta Y or La) and poly-per-fluorinated
ORF-[12 13 38 89-92] or similar aromatic ligands (ArF)[71 93 94] Compared to [B(C6F5)4]ndash and
other related borates these metallates offer the advantage of being easily accessible on a
preparative scale The [M(OC6F5)n]ndash-anions were shown to generate very active cationic
polymerization catalysts of better quality to those partnered with the [B(C6F5)4]ndash-anion[71 93
94]
9
[Nb(OC6F5)6]ndash[Nb(OC6F5)6]ndash
Fig A-6 Structure of [Nb(OC6F5)6]ndash as a representative example of a perfluorinated aromatic alkoxy metallate
[M(OArF)n]ndash shown as ball-and-stick model
However the oxygen atoms as well as CndashF bonds of the aryloxides OArF in [M(OArF)n]ndash are
prone to coordination and may therefore decompose
Two other important classes of WCAs have been established triflimides [N(SO2F)2]ndash and
[N(SO2CF3)2]ndash (Fig A-7) ndash derived from bis(fluorosulfonyl) amine[95-97] and
bis(trifluoromethylsulfonyl) amine[95] ndash and the analogous triflides [C(SO2F)3]ndash and
[C(SO2CF3)3]ndash which are based on the corresponding methanes[98-100]
[N(SO2CF3)2]ndash[N(SO2CF3)2]ndash
Fig A-7 Structure of the [N(SO2CF3)2]ndash anion shown as ball-and-stick model
10
These very robust anions are stable in water[101 102] and generate highly active catalysts for
various reactions e g Diels-Alder reactions[103-105] Friedel-Crafts acylations[106 107] and
others[108 109] But the most successful fields of application of these WCAs are
electrochemistry (eg in Li-ion batteries[110] or as electrolytes[111]) and ionic liquids[111]
Another last variation to get at least the most weakly coordinating anion has been achieved by
the substitution of ORF (RF = C(CF3)3) against OArF in [M(OArF)n]ndash Thus the generated
perfluorinated alkoxy aluminate [Al(ORF)4]ndash (and RF-variations from C(H)(CF3)2 to
C(CH3)(CF3)2) has been the starting point for new WCA chemistry of this kind of compounds
With the large number of peripheral CndashF bonds (36 in total) the [Al(ORF)4]ndash-anion is
together with [CB11(CF3)12]ndash presumably one of the least coordinating anions known
However the carborane species is explosive These alkoxyaluminates are representatives of
[M(ORF)n]ndash and [M(OArF)n]ndash and have been applied in our group since 1999 but were first
reported by Strauss et al in 1996[89] Especially the perfluorinated aluminate [Al(ORF)4]ndash (RF
= C(CF3)3 cf Fig A-8) serves as a very resistant anion even stable against heterolytic ion
separation in H2O and 6N HNO3 The CF3 groups provide a smooth and non-adhesive
Teflon-surface on the anion This stability against electrophilic attacks as well as weakly
coordinating ability may be further improved with the even bulkier fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash-anion (see also[112] Fig A-8) which has been recently synthesized
(see below) One of the major advantages of the aluminates is that they are easily accessible
with little synthetic effort on a preparative scale in form of Li+- Cs+- or Ag+-salts 100 g
within two days in common laboratories with well yield over 95 [12 90 113]
11
[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash[Al(ORF)4]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash
Fig A-8 Structures of the WCAs [Al(ORF)4]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) shown as ball-and-
stick model
Finally summarizing all the aspects mentioned before the general idea over years was to
synthesize the most chemically robust and weakly coordinating anion The last criterion has
been definitely achieved by halogenated carborane anions which are more strongly
coordinating than other WCAs Owning to their exceptional stability they allow the
preparation of very electrophilic cations that decompose all other currently known WCAs
Thus when a maximum stability towards electrophiles is desired the halogenated carborane-
based WCAs are certainly the best choice Of these the fluorinated derivates such as [1-
EtCB11F11]ndash are the least coordinating However if the electrophile is compatible with other
less coordinating WCAs the choice definitely goes to the use of [Al(ORF)4]ndash and [(RFO)3Alndash
FndashAl(ORF)3]ndash (RF = C(CF3)3)
In order to estimate the relative stabilities and coordinating abilities of all types of WCAs
theoretical calculations on coordination strength and redox stability have been made[114]
These allow the forecast for use and application of each WCA The most suitable model to
investigate the stability of fluorinated anions in our chemistry is the calculation of the fluoride
12
ion affinities (FIAs) of their parent Lewis acids A (Eq A-2) which were estimated on
thermodynamic grounds[115 116]
A(gas) + Fndash(gas) AFndash
(gas)∆H = ndashFIA
(Eq A-2)
The higher the FIA of the parent Lewis acid A of a given WCA the more stable it is against
decomposition on thermodynamic grounds KO Christe and D Dixon chose a computational
approach to obtain a larger relative Lewis acidity scale based on the calculation of the FIA in
an isodesmic reaction (number and type of bonds are not changed) with [OCF3]- and the
experimental FIA of OCF2 of 209 kJmol[117] Others used the same methodology[12 92 118-121]
Within this work calculations on Lewis acids were limited to relatively small systems
Aim of This Work
Investigations from our group showed that the fluorinated alkoxy aluminate anions
[Al(ORF)4]ndash (RF = C(CF3)3 C(H)(CF3)2 C(CH3)(CF3)2) fulfil the requirements for modern
WCAs with ease[17] They may be easily prepared from Li+-salts in high yields from the
adequate alcohols and LiAlH4[12 113] Experiments with these various [Al(ORF)4]ndash-anions
formed salts of different stability and coordination ability[12 29 90 92 122 123] Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreased The aim of the first part of this thesis was the investigations of new
bulky WCAs of the type of [Al(ORF)4]ndash (RF = C(R)(CF3)2 with R = Nonfluorinated bulky
organic residue) from their corresponding fluorinated lithium alkoxides LiORF or alcohols
HORF These alkoxidesalcohols were anticipated to be good building blocks and precursors
for novel weakly coordinating anions
13
F3C CF3
O
MO C
CF3
CF3
R
RF
HO C
CF3
CF3
R14 Li[Al(ORF)4]
M R+
+ H+ H2O + 14 AlX3
14 M[Al(ORF)4]
ndash 34 MX
14 LiAlH4
ndash H2
aliphatic solvent
M = Li MgXR = organic residue
aliphatic solvent
hexafluoracetone
Scheme A-1 General synthetic methods to prepare new WCAs of the type [Al(ORF)4]ndash
In the second and main part of this work the chemistry of the classical [Al(ORF)4]ndash WCAs
should be widened to anions of the type of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash (RF =
C(CF3)3) The latter fluorine bridged anion has already been synthesized by Krossing et
al[112] though in this work a new method should be developed and both anions isolated as
suitable salts to make them accessible for further chemistry The to our standard [Al(ORF)4]ndash
WCAs underlying Lewis acid Al(ORF)3 should be completely characterized and its property
as a very strong acid compared to already known classical Lewis acids eg by reactions with
fluoride complexes of strong Lewis acids such as BF3 PF5 and SbF5 Most projects have been
accompanied with quantum mechanical calculations
14
References to Chapter A
[1] W Beck K Suenkel Chem Rev 1988 88 1405 [2] C A Reed Acc Chem Res 1998 31 133 [3] S H Strauss Chem Rev 1993 93 927 [4] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [5] K Seppelt Angew Chem 1993 105 1074 [6] M Bochmann Angew Chem 1992 104 1206 [7] A J Lupinetti S H Strauss Chemtracts 1998 11 565 [8] A G Massey A J Park J Organometal Chem 1964 2 461 [9] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453 [10] T S Cameron I Krossing J Passmore Inorg Chem 2001 40 4488 [11] D Stasko A Reed Christopher J Am Chem Soc 2002 124 1148 [12] I Krossing Chem Eur J 2001 7 490 [13] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [14] R E LaPointe G R Roof K A Abboud J Klosin J Am Chem Soc 2000 122 9560 [15] V C Williams G J Irvine W E Piers Z Li S Collins W Clegg M R J Elsegood T B Marder
Organometallics 2000 19 1619 [16] E Y X Chen K A Abboud Organometallics 2000 19 5541 [17] I Krossing I Raabe Angew Chem Int Ed 2004 43 2066 I Krossing I Raabe Angew Chem 2004 116 2116 [18] S Seidel K Seppelt Science 2000 290 117 [19] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [20] S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem Int Ed 2007 46 6717
S Seidel K Seppelt C van Wuellen X Y Sun Angew Chem 2007 119 6838 [21] C A Reed K-C Kim R D Bolskar L J Mueller Science 2000 289 101 [22] K-C Kim C A Reed D W Elliott L J Mueller F Tham L Lin J B Lambert Science 2002 297
825 [23] P K Hurlburt J J Rack J S Luck S F Dec J D Webb O P Anderson S H Strauss J Am
Chem Soc 1994 116 10003 [24] A Reisinger F Breher D V Deubel I Krossing Chem Eur J 2007 [25] A Reisinger W Scherer I Krossing Chem Eur J 2007 [26] I Krossing A Reisinger Angew Chem Int Ed 2003 42 5919 I Krossing A Reisinger Angew Chem 2003 115 6099 [27] I Krossing J Am Chem Soc 2001 123 4603 [28] I Krossing L Van Wuellen Chem Eur J 2002 8 700 [29] T S Cameron A Decken I Dionne M Fang I Krossing J Passmore
Chem Eur J 2002 8 3386 [30] A Adolf M Gonsior I Krossing J Am Chem Soc 2002 124 7111 [31] I Krossing J Chem Soc 2002 500 [32] I Krossing A Bihlmeier I Raabe N Trapp Angew Chem Int Ed 2003 42 1531 I Krossing A Bihlmeier I Raabe N Trapp Angew Chem 2003 115 1569 [33] H P A Mercier M D Moran G J Schrobilgen C Steinberg R J Suontamo
J Am Chem Soc 2004 126 5533 [34] I Krossing I Raabe S Muumlller M Kaupp Dalton Trans 2007 [35] A Vij W W Wilson V Vij F S Tham J A Sheehy K O Christe
J Am Chem Soc 2001 123 6308 [36] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [37] N J Patmore C Hague J H Cotgreave M F Mahon C G Frost A S Weller Chem Eur J 2002
8 2088 [38] T J Barbarich S M Miller O P Anderson S H Strauss J Mol Cat A 1998 128 289 [39] S D Ittel L K Johnson M Brookhart Chem Rev 2000 100 1169 [40] G J P Britovsek V C Gibson D F Wass Angew Chem Int Ed 1999 38 428 G J P Britovsek V C Gibson D F Wass Angew Chem 1999 111 448 [41] S Mecking Coord Chem Rev 2000 203 325 [42] H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem Int Ed 1995
34 1143 H H Brintzinger D Fischer R Muelhaupt B Rieger R M Waymouth Angew Chem 1995 107
1255
15
[43] W E Piers Chem Eur J 1998 4 13 [44] C Zuccaccia N G Stahl A Macchioni M-C Chen J A Roberts T J Marks J Am Chem Soc
2004 126 1448 [45] M-C Chen J A S Roberts T J Marks J Am Chem Soc 2004 126 4605 [46] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [47] R J LeSuer W E Geiger Angew Chem Int Ed 2000 39 248 [48] F Barriere N Camire W E Geiger U T Mueller-Westerhoff R Sanders J Am Chem Soc 2002
124 7262 [49] N Camire U T Mueller-Westerhoff W E Geiger J Organomet Chem 2001 637-639 823 [50] N Camire A Nafady W E Geiger J Am Chem Soc 2002 124 7260 [51] P G Gassman P A Deck Organometallics 1994 13 1934 [52] P G Gassman J R Sowa Jr M G Hill K R Mann Organometallics 1995 14 4879 [53] M G Hill W M Lamanna K R Mann Inorg Chem 1991 30 4687 [54] L Pospisil B T King J Michl Electrochim Acta 1998 44 103 [55] P Wasserscheid W Keim Angew Chem Int Ed 2000 39 3772 P Wasserscheid W Keim Angew Chem 2000 112 3926 [56] A Boesmann G Francio E Janssen M Solinas W Leitner P Wasserscheid Angew Chem Int Ed
2001 40 2697 [57] T Welton Chem Rev 1999 99 2071 [58] J V Crivello Radiation Curing in Polymer Science and Technology 1993 2 435 [59] F Castellanos J P Fouassier C Priou J Cavezzan J Appl Polymer Science 1996 60 705 [60] H Gu K Ren O Grinevich J H Malpert D C Neckers J Org Chem 2001 66 4161 [61] H Li K Ren W Zhang J H Malpert D C Neckers Macromolecules 2001 34 2019 [62] K Ren J H Malpert H Li H Gu D C Neckers Macromolecules 2002 35 1632 [63] K Ren A Mejiritski J H Malpert O Grinevich H Gu D C Neckers Tetrahedron Lett 2000 41
8669 [64] F Kita H Sakata A Kawakami H Kamizori T Sonoda H Nagashima N V Pavlenko Y L
Yagupolskii J Power Sources 2001 97-98 581 [65] F Kita H Sakata S Sinomoto A Kawakami H Kamizori T Sonoda H Nagashima J Nie N V
Pavlenko Y L Yagupolskii J Power Sources 2000 90 27 [66] L M Yagupolskii Y L Yagupolskii J Fluorine Chem 1995 72 225 [67] N Ignatev P Sartori J Fluorine Chem 2000 101 203 [68] E Bernhardt G Henkel H Willner G Pawelke H Burger Chem Eur J 2001 7 4696 [69] J H Golden P F Mutolo E B Lobkovsky F J DiSalvo Inorg Chem 1994 33 5374 [70] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [71] F A R Kaul G T Puchta H Schneider M Grosche D Mihalios W A Herrmann J Organomet
Chem 2001 621 177 [72] L Jia X Yang C L Stern T J Marks Organometallics 1997 16 842 [73] L Jia X Yang A Ishihara T J Marks Organometallics 1995 14 3135 [74] J Zhou S J Lancaster D A Walker S Beck M Thornton-Pett M Bochmann J Am Chem Soc
2001 123 223 [75] S J Lancaster D A Walker M Thornton-Pett M Bochmann Chem Comm 1999 1533 [76] D Vagedes G Erker R Frohlich J Organomet Chem 2002 651 157 [77] S J Lancaster A Rodriguez A Lara-Sanchez M D Hannant D A Walker D H Hughes M
Bochmann Organomeallics 2002 21 451 [78] B T King J Michl J Am Chem Soc 2000 122 10255 [79] D M Van Seggen P K Hurlburt M D Noirot O P Anderson S H Strauss Inorg Chem 1992 31
1423 [80] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [81] K Moock K Seppelt Z Anorg Allg Chem 1988 561 132 [82] I B Sivaev A Kayumov A B Yakushev K A Solntsev N T Kuznetsov Koord Khim 1989 15
1466 [83] A Franken B T King J Rudolph P Rao B C Noll J Michl Collect Czech Chem Comm 2001
66 1238 [84] T Jelinek J Plesek S Hermanek B Stibr Collect Czech Chem Comm 1986 51 819 [85] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [86] Z Xie C-W Tsang E T-P Sze Q Yang D T W Chan T C W Mak Inorg Chem 1998 37
6444 [87] Z Xie C-W Tsang F Xue T C W Mak J Organomet Chem 1999 577 197
16
[88] B T King Z Janousek B Gruener M Trammell B C Noll J Michl J Am Chem Soc 1996 118 3313
[89] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[90] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [91] M Gonsior I Krossing Chem Eur J 2004 10 5730 [92] M Gonsior I Krossing N Mitzel Z Anorg Allg Chem 2002 628 1821 [93] M V Metz Y Sun C L Stern T J Marks Organometallics 2002 21 3691 [94] Y Sun M V Metz C L Stern T J Marks Organometallics 2000 19 1625 [95] Z Zak A Ruzicka Z f Kristallogr 1998 213 [96] R Appel G Eisenhauer Chem Ber 1962 95 2468 [97] B Krumm A Vij R L Kirchmeier J n M Shreeve Inorg Chem 1998 37 6295 [98] L Turowsky K Seppelt Inorg Chem 1988 27 2135 [99] G Kloeter H Pritzkow K Seppelt Angew Chem 1980 92 954
G Kloeter H Pritzkow K Seppelt Angew Chem Int Ed 1980 19 942 [100] Y L Yagupolskii T I Savina Zh Organi Khim 1983 19 79 [101] A I Bhatt I May V A Volkovich D Collison M Helliwell I B Polovov R G Lewin Inorg
Chem 2005 44 4934 [102] F Croce A DAprano C Nanjundiah V R Koch C W Walker M Salomon J Electrochem Soc
1996 143 154 [103] Y L Yagupolskii T I Savina I I Gerus R K Orlova Zh Organi Khim 1990 26 2030 [104] K Takasu N Shindoh H Tokuyama M Ihara Tetrahedron 2006 62 11900 [105] A Sakakura K Suzuki K Nakano K Ishihara Org Lett 2006 8 2229 [106] M Kawamura D-M Cui S Shimada Tetrahedron 2006 62 9201 [107] A K Chakraborti Shivani J Org Chem 2006 71 5785 [108] K Takasu T Ishii K Inanaga M Ihara K Kowalczuk J A Ragan Org Synth 2006 83 193 [109] P Goodrich C Hardacre H Mehdi P Nancarrow D W Rooney J M Thompson Ind Eng Chem
Res 2006 45 6640 [110] S Seki Y Kobayashi H Miyashiro Y Ohno A Usami Y Mita N Kihira M Watanabe N Terada
J Phys Chem B 2006 110 10228 [111] Z Fei D Kuang D Zhao C Klein W H Ang S M Zakeeruddin M Graetzel P J Dyson Inorg
Chem 2006 45 10407 [112] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [113] I Krossing A Reisinger Coord Chem Rev 2006 250 2721 [114] I Krossing I Raabe Chem Eur J 2004 10 5017 [115] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [116] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [117] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [118] S Brownridge I Krossing J Passmore H D B Jenkins H K Roobottom Coord Chem Rev 2000
197 397 [119] T S Cameron R J Deeth I Dionne H Du H D B Jenkins I Krossing J Passmore H K
Roobottom Inorg Chem 2000 39 5614 [120] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [121] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [122] I Krossing A Reisinger Eur J Inorg Chem 2005 1979 [123] A Decken H D B Jenkins B Nikiforov Grigori J Passmore Dalton Trans 2004 2496 [124] D Lentz K Seppelt Z Anorg Allg Chem 1983 502 83 [125] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451
17
B Attempts to synthesize WCAs of the type [Al(ORF)4]ndash
(RF = OndashC(R)(CF3)2 R = tBu and Mes (mesitylene))
B1 Lithium Alkoxides as precursors for WCAs
Throughout the last century main group and transition metal alkoxides played an important
role in chemistry mainly due to their application in organometallic syntheses and as
precursors for electronic or ceramic materials[1-3] It has been reported that Li-containing
complexes aggregate yielding ~12 general structural types[4-6] The factors that determine the
final structure of these Li species have been attributed to the choice of solvent (Lewis
basicity) used during their synthesis the electron-donating ability of the α-atom of the ligand
(C N O or X) the bonding ability of the ligand (mono- bi- tri- or polydentate) or the steric
bulk and number of the ligands (ndashX ndashOR ndashNR2)[4-7] The motivation has been the syntheses
of new fluorinated metal alkoxides[8 9] as precursors to new weakly coordinating anions
(WCAs) in alkoxy metalates [M(ORF)4]ndash[10] to complement (per-)fluorinated alkoxy residues
ORF = C(CF3)3 C(CF3)2R (R = H Me) with the bulky R = tBu or Mes (= 246-Me3C6H2)
presently used in our group The desired [Al(ORF)4]ndash WCAs appeared valuable synthetic
goals since they should be very stable towards electrophilic attack due to the steric shielding
provided by the bulky OC(CF3)2Mes ligand Moreover WCAs such as those in the aluminate
Li+[Al(ORF)4]ndash[10] evoke easily accessible Li+ cations which tend to be ldquonakedrdquo Such weakly
coordinated Li+ ions may even soluble in toluene and n-hexane[11] and are therefore active as
catalyst in organic transformations as Diels-Alder reactions 14-conjungated additions and
pericyclic arrangement reactions[11 12] The related Li+[Al(OC(CF3)2Ph)4]ndash was shown to be a
good catalyst for this purposes[11]
18
The most widespread synthesis[6] of Li-alkoxides LiOR is the reaction of the alkaline metals
or alkaline metal hydrides with alcohols RndashOH (R = organic) Due to the small and polarizing
Li+ ion the structures tend to be aggregated Li+Xndash (X = halide OR NR2) Monomeric ion
pairs of Li+Xndash only exist in the gasphase (X = halide[13] NR2[14]) which associate in
condensed phases with formation of ring molecules (LiX)n (n = 2 3 rarely 4 (types I II III))
infinite chains (LiX)infin (type IV) heterocubanes (CNLi = 3) (see type V) aggregated
heterocubanes (type VI) ladders (type VII) or even hexagonal prisms (type VIII in Fig B-1)
Li
X
X
Li
X
Li
X
Li Li
X
X
Li X
Li
Li X
X Li
Structure Type I Structure Type II Structure Type III
Li
X
Li
X
Li
X
Li
X X
Li X
Li
X Li
XLi
Structure Type IV Structure Type VI
X
Li X
Li
X Li
XLi
X
Li X
Li
X Li
XLi
Structure Type V
Li
X
X
Li
Li
X
Structure Type VII
X LiXLi
X LiX Li
Li X
XLi
Structure Type VIII
Fig B-1 General structural types of [Li+Xndash]n (X = halide OR NR2 R = alkyl aryl)
19
B11 Chasing an elusive alkoxide Attempts to synthesize [OC(tBu)(CF3)2]ndash
Scheme B-1 shows the identified products of the different reactions of hexafluoroacetone with
tBuLi or tBuMgX (X = Cl I) as tBu source
C
O
F3C CF3
(THF)3LiO(CF3)2OC(H)(CF3)2 (B-2)
in THF
A
B
C
D Et2O Et2O
Et2O
[Li(OC(H)(CF3)2]42Et2O (B-1) MgI2
2Et2O (B-3) +
(CF3)2(H)COMgCl2Et2O (B-4)
+ tBuLindash (CH3)2CCH2
1 n-hexane2 Et2O
+ tBuLindash (CH3)2CCH2
+ tBuMgI
+ tBuMgClndash (CH3)2CCH2
+ tBuLi+ CuI
E
Mixture discarded
Scheme B-1 Attempted syntheses of the new MORF alkoxides with RF = CtBu(CF3)2 isolated products
All attempted syntheses of the new alkoxide MORF did not succeed as anticipated In route A
hexafluoroacetone was condensed to a frozen solution of tBuLi in n-hexane at 77 K After
warming to 195 K and stirring overnight at room temperature the solvent was removed at 298
K by vacuum distillation and a colorless oil was isolated The oil was recrystallized from Et2O
and was identified by spectroscopy and x-ray analysis as [Li(OC(H)(CF3)2]42Et2O (B-1) (δ1H
((CF3)2CndashH) = 441 (sep)) The second route B proceeded similar to A but the solvent was
changed from n-hexane to a n-hexaneTHF mixture After addition of (CF3)2CO and warming
first to 195 K (2h) than to 298 K (12 h) the solvent was removed by vacuum distillation at
298 K The resulting yellow oil was recrystallized from THF The colorless crystals were
identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (δ1H ((CF3)2CndashH) = 441 (sep)) In
structure B-2 the two C(CF3)2 groups are dissimilar (δ19F (O2C(CF3)2) = ndash762 (s) δ19F
(OC(H)(CF3)2) = ndash822 (s)) Thus it appears that the solid state structure remains intact in
20
solution Also the next route C with the Grignard tBuMgI did not proceed as hoped and the
only identified product was a large amount of MgI22Et2O (B-3)
Route D employed commercially available Grignard reagent tBuMgCl dissolved in Et2O was
frozen to 77 K Hexafluoroacetone was condensed onto the frozen liquid and allowed to
slowly warm with stirring to 298 K After removing the solvent a white precipitate was
formed On the basis of the NMR-data and the weight balance this white precipitate was
assigned as (CF3)2(H)COMgCl2Et2O (B-4) (δ1H ((CF3)2CndashH) = 538 (br sept) δ19F
C(CF3)2 = ndash751 (s)) In route E CuI was added to the tBuLi in order to use the gentler
organocuprates as alkylating agent[15] 1H NMR spectroscopic analyses of several reactions
revealed the presence of complex mixtures which were discarded (several broad singlets at
δ1H asymp 43 (CF3)2C-H ) several singlets at δ1H asymp 12 (tBu ))
In summary we demonstrated that neither the reagent tBuLi nor the Grignards tBuMgX add to
the electrophilic carbonyl atom of (CF3)2CO In general both rather act as Hndash donors Thus
unfortunately the preparation of [OCtBu(CF3)2]ndash proved impossible with all conditions tried
The solvent dependent formation of B-1 and B-2 may be understood by the initial addition of
Hndash to (CF3)2CO to give the [(CF3)2C(H)O]ndash-alkoxide which in THF may coordinate another
(CF3)2CO to give B-2 (Scheme B-2)
F3C C
O-
CF3
H
F3CC
CF3
OF3C CF3
O
H
F3C CF3
O-
+
Scheme B-2 Coordination of a hexafluoroacetone molecule by the alkoxide [(CF3)2C(H)O]ndash produces the anion
in B-2
21
The reason for this solvent selectivity may be due to the stronger donor capacity of THF that
breaks up the tetrameric structure B-1 and thus increases the nucleophilicity of the alkoxide
oxygen atom
B12 Crystal Structures
The crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) is shown in Fig B-2 Compound B-1
forms a slightly distorted (LindashO)4 heterocubane (lt(OndashLindashO)av 9434deg lt(LindashOndashLi)av 8532deg)
Two of the four Li atoms are coordinated by Et2O molecules Such a heterocubane structure is
a general structural feature of Li alkoxides and is due to the high electrophilicity of the small
lithium ion In this structure Li is either coordinated by four oxygen atoms (d(LindashO) = 187 Aring
to 201 Aring) or it additionally interacts with fluorine atoms (d(LindashF) = 215 Aring to 238 Aring)
Fig B-2 Section of the crystal structure of [Li(OC(H)(CF3)2]42Et2O (B-1) shown as Ortep model The atoms of
the structure are shown as thermal ellipsoids with a probability of 20 Only H atoms are shown as small circles
of an arbitrary scale
Some selected distances [Aring] and angles [deg] of B-1 Li(3A)ndashO(4A) 1962(9) Li(3A)ndashO(3A)
1965(10) Li(3A)ndashO(1A) 1984(10) Li(2A)ndashO(4A) 1976(9) Li(2A)ndashO(3A) 1962(9)
22
Li(2A)ndashO(2A) 2016(10) Li(1A)ndashO(4A) 1950(10) Li(1A)ndashO(2A) 1878(10) Li(1A)ndashO(1A)
1946(9) Li(3A)ndashO(6A) 1927(10) Li(2A)ndashO(5A) 1957(9) O(4A)ndashC(10A) 1380(6)
Li(4A)ndashF(7A) 2171(10) Li(1A)ndashF(6A) 2157(10) Li(1A)ndashF(22A) 2388(10) CndashC 1273(1)ndash
1525(9) (Oslash 1453(1)) CndashF 1306(9)ndash1374(8) (Oslash 1334(9))
In the related structure [Li(OCH2CF3)]4(THF)3[16] the LindashO distances range from 187 to 197
[Aring] The coordinated neutral Et2O molecules exhibit rather short LindashO distances (d(LindashO) =
192 195 Aring cf d(LindashOalkoxide) = 187 to 201 [Aring]) This demonstrates the weakly basic nature
of the alkoxide oxygen atoms that ndash although being negatively charged and thus expected to
interact more strongly with the Li atoms ndash exhibit similar LindashO bond lengths as the neutral
and therefore on first sight weaker oxygen donor Et2O Fig B-3 shows the molecular
structure of B-2 In contrast to B-1 B-2 exhibits a structure in which one hexafluoroacetone
molecule is coordinated to a [(CF3)2C(H)O]ndash alkoxide (see Fig B-3) It is the first known
structure of a fluorinated alkoxy-alkoxide
Fig B-3 Molecular structure of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) shown as Ortep model The atoms of the
structure are shown as thermal ellipsoids with a probability of 25 The H atoms are shown as small circles of
an arbitrary scale
23
Selected bond lengths [Aring] of B-2 Li(1)ndashO(1) 1810(7) Li(1)ndashO(4) 1950(7) Li(1)ndashO(5)
1968(8) Li(1)ndashO(3) 1938(8) O(1)ndashC(1) 1282(5) C(1)ndashO(2) 1507(5) O(2)ndashC(2) 1417(5)
C(1)ndashC(4) 1559(6) CndashF 1300(7)ndash1345(6) (Oslash 132(3)) Li(1)ndashO(1)ndashC(1) 1571(3) C(1)ndash
O(2)ndashC(2) 1144(3) O(1)ndashC(1)ndashO(2) 1149(3)
The LindashO distances to the coordinated THF donors are similar and average to 195 Aring The Li-
alkoxide distance Li(1)ndashO(1) is by 014 Aring shorter than the other LindashO separations The
distance between C(1)ndashO(1) (128 Aring) is much shorter than C(1)ndashO(2) (151 Aring) This may be
compared to the average C=O distance in acetone (121 Aring)[17] as well as the average CndashO
distance in B-1 of 138 Aring The unusual CndashO distances in B-2 may be rationalized by the
following resonance structures (Scheme B-4)
(THF)3Li
OC
O
F3CCF3
C
HCF3
CF3
(THF)3Li
O
CF3C CF3
O
C
H
F3C CF3
I II
Scheme B-4 Two important resonance structures to rationalize the structural parameters of B-2
In the resonance structure I all three CndashO bond lengths tend to be similar but according to structure II
significantly different CndashO bond lengths with bond orders gtgt 10 and ltlt 10 can be expected It appears that II
has more weight to describe compound B-2
B13 DFT Calculations
To understand if the observed Hndash addition of tBuLi to the carbonyl atom of
hexafluoroacetone is due to kinetics (9 equivalent H atoms for Hndash addition and isobutene
24
elimination) or thermodynamics we fully optimized[18 19] the structures of tetrameric (tBuLi)4
hexafluoroacetone as well as the Hndash and tBundash addition products and the eliminated isobutene
at the BP86SV(P) level of theory[20 21] with the program Turbomole Then the
thermodynamics of the two possible reactions with inclusion of zero point energy have been
analyzed thermal contributions to the enthalpyentropy and solvation effects with the
COSMO[22 23] model (Table B-1)
Table B-1 Thermodynamics of Hndash and tBundash addition to hexafluoroacetone (all values are given in kJ molndash1)
Reaction ∆rΗdeg ∆rGdeg ∆solvGdeg
(tBuLi)4 + (F3C)2CO rarr (F3C)2(tBu)COLi ndash294 ndash229 ndash211 (tBuLi)4 + (F3C)2CO rarr (F3C)2(H)COLi + C4H8 ndash235 ndash234 ndash227
The calculated thermodynamics as in Table B-1 show that the preference of Hndash over tBundash
addition to hexafluoroacetone is not only kinetic but also thermodynamic Thus it appears
that other routes than MtBu addition have to be used to induce [OCtBu(CF3)2]ndash formation
Summarizing the chemistry of the attempts to synthesize a new lithium alkoxide
Li+[OC(R)(CF3)2]ndash (R = tBu) very briefly one can gather that other routes have to be found
However the straight forward but unexpected synthesis of the first fluorinated alkoxy-
alkoxide B-2 may be of importance for further WCA syntheses if a weak oxygen donor is
desired in the periphery of the WCA
B2 The fluorinated lithiumalkoxide LiORF (RF = C(CF3)2Mes) the alcohol
RFOH and attempts to use them as precursors for new WCAs
In further attempts the preparation and structural characterization of compounds containing
the ORF residue (RF = C(CF3)2Mes) has been undertaken ie structural variations of LiORF
25
the alcohol HOndashRF and first attempts to use the alkoxidealcohol for the preparation of WCAs
of type [M(ORF)4]- (M = Al Ga) by reaction with MBr3LiMH4
B21 Syntheses and Crystal Structures
B211 Synthesis of LiMesOEt2 Initially the starting compound MesndashLiOEt2 was prepared
according to the literature[23b] by lithiation of bromomesitylene in Et2O as a white powder in
90 yield
Br
+ n-BuliEt2O
LiOEt2
+ n-BuBr
LiMesOEt2(Eq B-1)
B212 Synthesis of [LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4 (B-5) was formed by the
reaction of MesndashLiOEt2 and gaseous (CF3)2CO (Eq B-2) The latter was condensed onto the
frozen toluene solution of MesndashLiOEt2 After stirring for 4 hours at 213 K the mixture was
allowed to slowly reach room temperature The resulting light yellow solid product was
washed recrystallized from n-pentane isolated and spectroscopically characterized
LiOEt2
+ 4
F3C
O
CF3
toluene[LiOC(CF3)2Mes]4 (B-5) (Eq B-2)4
26
The lithium alkoxide 5 crystallizes in the rare structural type III (cf Fig B-1) the central
structural element is a puckered eight membered (LindashO)4 ring (Fig B-4)
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig B-4 Molecular structure of [LiOC(CF3)2Mes]4 (B-5) at 140 K with thermal displacement ellipsoids showing
50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashO(1) 1802(9)
Li(1)ndashO(2) 1821(9) Li(1)ndashC(1) 2744(10) Li(1)ndashC(13) 2681(10) Li(1)ndashC(16) 2791 Li(1)ndashC(21) 2597(9)
Li(2)ndashO(1)rsquo 1857(9) Li(2)ndashO(2) 1852(8) O(1)ndashC(1) 1364(5) C(1)ndashC(4) 1567(6) O(2)ndashC(13) 1361(5)
C(13)ndashC(14) 1561(7) C(13)ndashC(15) 1546(7) C(13)ndashC(16) 1562(6) Li(2)ndashF(2)rsquo 2123(9) Li(2)ndashF(4)rsquo
2261(10) Li(2)ndashF(10)rsquo 2787(1) Li(2)ndashF(8)rsquo 2155(10) (CndashF)av 1331(7) O(1)ndashLi(1)ndashO(2) 1382(5) Li(1)ndash
O(1)ndashLi(2)rsquo 1211(4) Li(1)ndashO(2)ndashLi(2) 1157(4) O(2)ndashLi(2)ndashO(1)rsquo 1273(5) C(1)ndashO(1)ndashLi(1) 1195(4) C(13)ndash
O(2)ndashLi(1) 1140(4) O(1)ndashC(1)ndashC(3) 1093(3) O(1)ndashC(1)ndashC(4) 1120(4) C(3)ndashC(1)ndashC(4) 1081(4) O(2)ndash
C(13)ndashC(14) 1042(3) O(2)ndashC(13)ndashC(16) 1108(4) C(15)ndashC(13)ndashC(16) 1102
Thin plate-shaped colorless crystals of [LiOC(CF3)2Mes]4 (B-5) (Fig B-4) were obtained by
crystallization of a n-pentane solution at 253 K The centrosymmetric eight-membered ring
consists of an alternating arrangement of Li and O atoms where two of the four electrophilic
and small Li atoms are six-coordinated (LiO2F4 2+4 coordination) and the other two approach
a linear arrangement with some weak residual LindashMes interactions (LindashC 2597 - 2791 Aring
2703 Aring(av)) The tetrameric structure of this lithium organyl is untypical since such lithium
27
alkoxides tend to crystallize in the heterocubane (LiOR)4 structure of type V Probably the
steric demand of the mesitylene residues forces the coordination of the four LindashO units into a
ring shape where the average LindashO bonds are 1854 Aring (1802 - 1857 Aring) The OndashLindashO bond
angles are on average larger than 120deg (1328deg (av)) and the LindashOndashLi bond angles tend to be
smaller on average than 120deg (1184deg (av)) The intramolecular contact of Li(2) to one F atom
of each CF3 group (2331 Aring (av) range 2123 Aring to 2787 Aring) elongates the corresponding CndashF
bond distances by 0026 Aring (av) in comparison to the other CndashF bonds (1323 Aring (av))
B213 Synthesis of [LiOC(CF3)2Mes]4[LiF]2 (B-6) [LiOC(CF3)2Mes]4[LiF]2 (B-6) was
formed by the reaction of [LiOC(CF3)2Mes]4 and AlBr3 in n-hexane at 273 K In an poorly
understood sequence an F-atom from the alkoxide is removed rather than that AlBr3 reacts by
metathesis to the lithium alkoxy aluminate Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) In the course
of the decomposition the [LiF]2 complex was formed (Eq B-3)
F3C CF3
OLi
+AlBr3
n-hexane
ndash3LiBr
Li[Al(OC(CF3)2Mes]4 (Eq B-3)
Li[OC(CF3)2Mes]4[LiF]2 (B-6)
yield 28
4
Further routes to Li+[Al(ORF)4]ndash (RF = C(CF3)2Mes) were investigated The reaction in
toluene led to an impure and decomposed non assignable red product mixture Several
28
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
F9
Li3C13C14
C16
F5lsquo C3lsquoC1lsquo
O1lsquo
Li1lsquoF13
O2
Li1
F13lsquoO2lsquo
Li3lsquo
O1C1C4
C3C2
F5 F9lsquo
Li2lsquo
Li2
C24
C12
C12lsquo
C24lsquo
C13lsquo
attempts with various conditions (order of adding the products temperature solvents) did not
lead to the desired product Li+[Al(ORF)4]ndash and the only clear result was formation of B-6
Thin plate-shaped colorless crystals of centrosymmetric [LiOC(CF3)2Mes]4[LiF]2 (B-6) (Fig
B-5) were obtained by crystallization from n-hexane solution at 253 K
Fig B-5 Molecular structure of [LiOC(CF3)2Mes]4[LiF]2 (B-6) at 140 K with thermal displacement ellipsoids
showing 50 probability Selected bond lengths and interactions are given in [Aring] and angles in [deg] Li(1)ndashF(13)rsquo
1940(9) Li(1)ndashF(13) 1947(9) Li(1)ndashO(1) 1974(9) Li(1)ndashO(2) 1998(9) Li(1)ndashC(24) 3273 Li(1)ndashC(12)
3340 Li(2)ndashC(24) 2837 Li(2)ndashC(12) 2809 Li(2)ndashC(1) 3133 Li(2)ndashC(13) Li(3)ndashC(14) 2845 Li(3)ndashC(1)
2894 Li(2)ndashF(13) 1841(9) Li(2)ndashO(1) 1919(10) Li(2)ndashO(2)rsquo 1928(10) Li(3)ndashF(13) 1843(9) Li(3)ndashO(1)rsquo
1976(10) Li(3)ndashF(5)rsquo 1979(9) Li(3)ndashF(9) 1982(9) Li(3)ndashO(2) 1986(9) F(13)ndashLi(1)rsquo 1940(9) O(1)ndashC(1)
1392(6) O(1)ndashLi(3)rsquo 1976(10) O(2)ndashC(13) 1373(6) O(2)ndashLi(2)rsquo 1928(10) C(1)ndashC(2) 1549(7) C(1)ndashC(3)
1568(7) C(1)ndashC(4) 1572(7) F(13)rsquondashLi(1)ndashF(13) 866(4) F(13)rsquondashLi(1)ndashO(1) 934(4) F(13)ndashLi(1)ndashO(1)
903(4) F(13)rsquondashLi(1)ndashO(2) 907(4) F(13)ndashLi(1)ndashO(2) 924(3) O(1)ndashLi(1)ndashO(2) 1751(5) F(13)ndashLi(2)ndashO(1)
954(4) F(13)ndashLi(2)ndashO(2)rsquo 961(4) O(1)ndashLi(2)ndashO(2)rsquo 1022(4) F(13)ndashLi(3)ndashO(1)rsquo 965(4) F(13)ndashLi(3)ndashF(5)rsquo
1069(4) O(1)rsquondashLi(3)ndashF(5)rsquo 790(4) F(13)ndashLi(3)ndashF(9) 1129(5) O(1)rsquondashLi(3)ndashF(9) 1506(5) F(5)rsquondashLi(3)ndashF(9)
928(3) F(13)ndashLi(3)ndashO(2) 960(4) O(1)rsquondashLi(3)ndashO(2) 981 (4) F(5)rsquondashLi(3)ndashO(2) 1571(5) F(9)ndashLi(3)ndashO(2)
785(3) Li(1)rsquondashF(13)ndashLi(1) 934(4) Li(2)rsquondashO(2)ndashLi(3) 790(4) Li(2)rsquondashO(2)ndashLi(1) 844(4) Li(3)ndashO(2)ndashLi(1)
830(4) O(1)ndash(1)ndashC(2) 1078(4) O(1)ndashC(1)ndashC(3) 1041(4) C(2)ndashC(1)ndashC(3) 1078(4) O(1)ndashC(1)ndashC(4) 1119(4)
29
C(2)ndashC(1)ndashC(4) 1107(4) C(3)ndashC(1)ndashC(4) 1141(4) O(2)ndashC(13)ndashC(16) 1119(4) O(2)ndashC(13)ndashC(14) 1039(4)
C(16)ndashC(13)ndashC(14) 1150(4)
The asymmetric unit consists of two lithium alkoxy- and one lithium fluoride formula units
where the twelve LindashO bonds and eight LindashF bonds of the symmetry generated complete
molecule form an almost ideal double heterocubane with an average LindashO bond distance of
1964 Aring (1919 - 1986 Aring) and two short LindashF distances at 1841 and 1843 Aring as well as two
longer at 1940 and 1947 Aring The OndashLindashO angles of each cube are larger (981 - 1022deg
1002deg av) than the LindashOndashLi angles (790 - 844deg 821deg av) Also the O(1)ndashLi(1)ndashO(2) angle
of 1751deg along the center-line proves the slight distortion of this double cage The two central
cubes are each shielded by two C(CF3)2Mes groups where one F atom of every second CF3
group forms an intramolecular LindashF contact (1979 Ǻ and 1982 Aring) Several weak residual Lindash
Mes interactions saturate the six times coordinated Li(1) (LindashC 3273 - 3340 Aring (3307 Aring(av))
and the seven times coordinated Li(2) and Li(3) (LindashC 2837 - 3178 Aring (2949 Aring(av)) The
numerous LindashF contacts are in very good agreement with other known structures of
fluorinated lithium[4] and the homologous sodium alkoxides[24-26] In the comparable
heterocubane structure of (LiORrsquo)4 (Rrsquo = C(CF3)3)[9] the analogous LindashF contacts are longer
and at 242 Aring (av)[9]
B214 Synthesis of HOC(CF3)2Mes The general idea of the preparation of the alcohol
HOC(CF3)2Mes was to achieve the synthesis of the lithium alkoxy aluminate Li+[Al(ORF)4]ndash
(RF = C(CF3)2Mes) by reaction with LiAlH4 in analogy to published procedures[10 11] The
alcohol was formed by the acidic hydrolysis (2M HCl) of the fluorinated lithium alkoxide
LiOC(CF3)2Mes under normal atmospheric conditions The alcohol was separated from the
aqueous phase by extraction with fluorobenzene Then the alcohol was distilled (bp = 393
K 001 mbar inert conditions) dried and isolated as a colorless liquid (yield 28 )
30
CF3F3C
OLi
+ 2M HClndashLiCl
CF3F3C
OH
4
4 (Eq B-4)
The spectroscopic analyses of HOndashC(CF3)2Mes are as expected Moreover
cyclovoltammograms of the alcohol and the redox-anchored lithium salt LiOC(CF3)2Mes in
the solvent mixture PCECDMCtoluene = 20205010 in 1M LiPF6 were recorded It was
observed that even at very low potentials during reduction no evolution of hydrogen
occurred (Eq B-5) This unusual behavior was ascribed to the bulkiness of RF and is in
agreement with the inertness towards reaction with LiAlH4 Therefore the proposed synthesis
of Li+[Al(ORF)4]ndash (Eq B-5) did not lead to success no reaction could be observed
CF3F3C
OH
4 + LiAlH4
various solvents including PhndashF and Et2O
ndash4H2
Li+[Al(ORF)4]ndash (Eq B-5)
ORF
Further attempts to prepare Li+[Al(ORF)4]ndash were also done in Et2O with dissolved LiAlH4 but
no reaction was observed Overall it appears that novel RF residue is too bulky to coordinate
31
four times to the (smaller) aluminum atom Even coordinating solvents like Et2O did not
support to the formation of Li+[Al(ORF)4]ndash from LiAlH4 and 4 RFndashOH
B215 Synthesis of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) It was tried to synthesize
the analogous lithium alkoxygallate as in equation B-3 but replacing AlBr3 for GaBr3
Gallium is a bit larger than aluminum and a somewhat weaker Lewis acid so it was hoped to
overcome the fluoride abstraction as found by reaction with AlBr3 However the synthesis
only led to the mixed bromo-alkoxy-gallate B-7 Although fluoride abstraction did not occur
it appears that the ORF residue is also too bulky for Gallium to form the tetrasubstituted
[Ga(ORF)4]- structure Colorless crystals of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) (Fig
B-6) were obtained by crystallization from a dichloroethane solution at 253 K in good yield
The solid-state structure contains half a molecule in the asymmetric unit The central
structural feature of B-7 is a centrosymmetric almost square planar LiO2Ga ring which
contains a lithium atom that is additionally coordinated by one solvent molecule
dichloroethane The LindashO distance is 1995 Aring the GandashO distance is 1883 Aring
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Fig B-6 Molecular structure of Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) at 140 K with thermal
displacement ellipsoids showing 50 probability Selected bond lengths and interactions are given in [Aring] and
angles in [deg] Li(1)ndashO(1) 1991(5) Br(1)ndashGa(1) 23088(4) Ga(1)ndashO(1) 18832(17) Cl(1)ndashC(13) 1782(3) Cl(1)ndash
Li(1) 2641(5) Li(1)ndashC(12) 2945 Ga(1)ndashF(2) 3189 Ga(1)ndashF(5) 3139 O(1)ndashC(1) 1406(3) O(1)rsquondashGa(1)ndashO(1)
32
8507(11) O(1)rsquondashGa(1)ndashBr(1)rsquo 11323(5) O(1)ndashGa(1)ndashBr(1)rsquo 11848(5) Br(1)rsquondashGa(1)ndashBr(1) 10752(2) C(13)ndash
Cl(1)ndashLi(1) 10567(14) Ga(1)ndashO(1)ndashLi(1) 9772(14) O(1)ndashLi(1)ndashO(1)rsquo 795(3) O(1)ndashLi(1)ndashCl(1) 11030(6)
O(1)rsquondashLi(1)ndashCl(1) 14905(6) Cl(1)ndashLi(1)ndashCl(1)rsquo 7688(18) C(1)ndashO(1)ndashLi(1) 1251(2) O(1)rsquondashGa(1)ndashLi(1)
4254(5) O(1)ndashLi(1)ndashGa(1) 3974(13)
The slightly distorted square exhibits an OndashGandashO angle that is larger (8507deg) than the OndashLindash
O angle (795deg) Both are smaller than the LindashOndashGa angle (9772deg) The two remaining free
coordination sites of the sixfold coordinated Li and eightfold coordinated Ga atoms are
occupied by a C2H4Cl2 molecule (coordinated via the Cl atoms) two Br atoms and two weak
LindashC contacts (LindashC 2945 Aring) as well as four weak GandashF contacts (GandashF 3139 - 3189 Aring
(3164 Aring av) The CndashCl bond lengths in the coordinated C2H4Cl2 molecule are with 1781 Aring
similar to the distance of 1791 in free C2H4Cl2[28] The GandashBr (2309 Aring) and the GandashO
distances are comparable and in good agreement to the GandashBr bond lengths in
[GaBr4]ndashPh2PPPh3+[29] (2322 Aring av) and to the GandashO distances (1883 Aring) in
[Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I) (1811 Aring av)[30] This also fits to the (LindashOndashGandashO) ring
in [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl] (=II) where the the LindashO (1983 Aring) and GandashO
(1872 Aring) bond lengths are nearly equivalent[31] In B-7 it appears that the small and hard Li+
cation coordinates more readily to the harder O-atoms (and not to the softer and much more
accessible Br-atoms)
GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)GaO
GaO
OCMe2Et
OCMe2Et
EtMe2CO
EtMe2CO
CMe2Et
CMe2Et
(=A)O
SiMe3
Ga LiO
THF
THF
Cl
(Me3Si)2N
SiMe3
(=B)(I) (II)
Fig B-9 Structures of [Ga(microndashOCMe2Et)(OCMe2ndashEt)2]2 (=I)[30] and [Li(THF)2][GaN(SiMe3)2(OSiMe3)2Cl]
(=II)[31] compared to B-7
33
B3 Conclusion
It was attempted to synthesize the alkoxide [OC(tBu)(CF3)2]ndash by the reaction of tBuM-
reagents (M=Li MgX) with hexafluoroacetone In all attempted syntheses ndash also supported
by theoretical DFT calculations ndash it was shown that [H]ndash addition is kinetically and
thermodynamically favored over [tBu]ndash addition Thus compounds like
[(Li(OC(H)(CF3)2]42Et2O (B-1) and (CF3)2(H)COMgClsdot(OEt2)2 (B-4) formed An
unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) an addition
compound built from [(CF3)2C(H)O]ndash and hexafluoroacetone which may be of importance for
further WCA syntheses Furthermore the complete structural characterizations of
[LiOC(CF3)2Mes]4 (B-5) [LiOC(CF3)2Mes]4[LiF]2 (B-6) and
Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] (B-7) were achieved B-5 could be prepared in large
scale and with excellent yields it is a rare example of a Li-alkoxide that does not adopt a
heterocubane structure As a side reaction with AlBr3 the LiF-complex B-6 with a double
heterocubane structure formed The alkoxide could be readily hydrolyzed to the respective
bulky alcohol which did not react with LiAlH4 and did not liberate H2 upon electrochemical
reduction All attempts to synthesize WCAs from these starting materials failed reactions to
prepare Li+[Al(ORF)4]ndash from AlBr3 or LiAlH4 did not lead to success Apparently the bulk of
the C(CF3)2Mes residue is to large to allow incorporation to the desired aluminate Similarly
the respective [Ga(ORF)4]ndash could not be prepared and only the disubstituted
dichloroethanecomplex B-7 could be isolated According to a search in the CSD database the
latter is the first account of a non-heterocubane Li-Chloroalkane complex Complex B-7
shows that the hard Li+ cation prefers coordination of the hard but poorly accessible oxygen
atom over the soft but easily accessible bromine atoms
34
References to Chapter B
[1] L G Hubert-Pfalzgraf Coord Chem Rev 1998 178-180 967 [2] L G Hubert-Pfalzgraf H Guillon Appl Organomet Chem 1998 12 221 [3] M Veith S Weidner K Kunze D Kaefer J Hans V Huch Coord Chem Rev 1994 137 297 [4] T J Boyle D M Pedrotty T M Alam S C Vick M A Rodriguez Inorg Chem 2000 39 5133 [5] F Pauer P P Power Lithium Chemistry 1995 295 [6] A-M Sapse D C Jain K Raghavachari Lithium Chemistry 1995 45 [7] E Weiss Angew Chem 1993 105 1565 [8] A Reisinger D Himmel I Krossing Angew Chem Int Ed 2006 45 6997
A Reisinger D Himmel I Krossing Angew Chem 2006 118 7153 [9] A Reisinger N Trapp I Krossing Organometallics 2007 26 2096 [10] I Krossing Chem Eur J 2001 7 490 [11] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss
Organometallics 1996 15 3776 [12] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Organic Lett 2001 3
2375 [13] J-G Gai Y Ren Int J Quantum Chem 2007 107 1487 [14] D B Grotjahn P M Sheridan I A Jihad L M Ziurys J Am Chem Soc 2001 123 5489 [15] J A Barth Organikum 20th Ed 1996 546 [16] T J Boyle T M Alam K P Peters M A Rodriguez Inorg Chem 2001 40 6281 [17] Typical interatomic distances International Tables of Crystallography Vol C 1999 797 [18] R Ahlrichs M Baer M Haeser H Horn C Koelmel Chem Phys Lett 1989 162 165 [19] M von Arnim R Ahlrichs J Chem Phys 1999 111 9183 [20] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [21] M Levy J P Perdew J Chem Phys 1986 84 4519 [22] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [23] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [23b] N Auner U Klingebiehl Synthetic Methods of Organometallic and Inorganic Chemistry Vol 2 1995 [24] R E A Dear W B Fox R J Fredericks E E Gilbert D K Huggins Inorg Chem 1970 9 2590 [25] J A Samuels K Folting J C Huffman K G Caulton Chem Mater 1995 7 929 [26] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Amer Chem Soc 1993 115 5093 [27] B Speiser Chemie in unserer Zeit 1981 15 62 [28] D R Lide CRC Handbook of Chemistry and Physics 76th ed 1995-1996 [29] M Sigl A Schier H Schmidbaur Z Naturforsch B Chem Sci 1998 53 1313 [30] M Valet D M Hoffman Chem Mater 2001 13 2135 [31] S T Barry D S Richeson Chem Mater 1994 6 2220
35
C A Highly Hexane Soluble Lithium Salt and other Starting
Materials of the Fluorinated Weakly Coordinating Anion
[Al(OC(CF3)2(CH2SiMe3))4]ndash
In this chapter the successful synthesis and characterization of a new lithium aluminate is
described This long-chained bulky lithium salt Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash is anticipated
to be a good candidate for Li ion catalysis Earlier it was shown[1 2 3] that given good WCAs
very low concentrations of the Li+[WCA]ndash catalyst (001 - 01M) are sufficient to promote
reactions Lithium salts of [Al(ORF)4]ndash (RF = C(Ph)(CF3)2)[1] [Nb(ORF)6]ndash (RF =
C(H)(CF3)2)[2] [CB12Me12]ndash[3] were used for such transformations Krossing and coworkers
have already shown that poly- or perfluorinated alkoxy aluminate anions [Al(ORF)4]ndash with RF
= C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 are useful reagents[4 5]
Problematic for anion coordinationdecomposition are the oxygen atoms of the aluminates
with smaller RF which represent the most basic sites of these aluminates Krossing et al
showed that with increasing bulk of the fluorinated alkyl residues the coordinative ability of
the anions decreases (Fig C-1)
RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3RF = C(H)(CF3)2 RF = C(CH3)(CF3)2 RF = C(CF3)3
Fig C-1 Space filling models of the three commonly in our group used alkoxy aluminate anions [Al(ORF)4]ndash
with RF = C(H)(CF3)2 C(CH3)(CF3)2 and C(CF3)3 The anions are taken from corresponding silver compounds[5]
Arrows mark the sites most likely to be attacked by small and polarizing cations
36
In this respect it was anticipated that an anion with ORF = OC(CF3)2(CH2SiMe3) should be
more stable as the bulky ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and protects them
from electrophilic attack Due to the absence of szligndashH atoms in the ndashCH2SiMe3 residue it is
known to be a good ligand in transition metal chemistry and thus should also be useful to
stabilize WCA salts of electrophilic cations Its aliphatic character was expected to induce
high solubility in non polar solvents which could be favorable for Li ion catalysis[1 2 3]
C1 Syntheses
The synthesis of the new lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
proceeds by three successive steps which are shown in equations C-1 to C-3 The first step is
the known preparation of LiCH2SiMe3 (sublimed twice) which was reacted with
hexafluoroacetone gas by condensing it onto a frozen solution of LiCH2SiMe3 in n-hexane
Four equivalents of the in quantitative yield resulting lithium alkoxide LiOC(CF3)2CH2SiMe3
(C-1) then react with AlBr3 giving the desired lithium alkoxy aluminate product
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) and lithium bromide This last step also proceeds in n-
hexane as solvent and revealed that the product C-2 is highly soluble in this aliphatic solvent
Thus C-2 may be isolated by simple filtration from insoluble LiBr
2Li + ClCH2SiMe3 LiCH2SiMe3ndashLiCl
LiCH2SiMe3 + (CF3)2CO LiOC(CF3)2CH2SiMe3 (C-1)
Li+[Al(OC(CF3)2CH2SiMe3)4]ndash (C-2)ndash3LiBr
Et2O
n-hexane
(Eq C-1)
(Eq C-2)
(Eq C-3) 4LiOC(CF3)2CH2SiMe3+AlBr3
37
The lithium aluminate C-2 may also be prepared by a one pot reaction whereby four
equivalents of the as prepared lithium alkoxide LiOC(CF3)2CH2SiMe3 (C-1) (Eq C-2)
directly react in situ with AlBr3 (Eq C-3) Both compounds LiOC(CF3)2CH2SiMe3 (C-1) and
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) are highly soluble in non-polar (eg aliphatic
hydrocarbons toluene) as well as in polar (eg acetonitrile) solvents The yield of C-2 is
better if synthesized by the one pot reaction (64 vs 53 )
Crystalline LiOC(CF3)2CH2SiMe3 (C-1) and Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) were
characterized by NMR IR and Raman spectroscopy Their NMR data are given below in
Table C-1 which also includes the [Ph3C]+ salt C-3 which was prepared by in situ NMR scale
reactions according to Eq C-4
[Li]+[A]ndash + Ph3CndashCl [Ph3C]+[A]ndashCD2Cl2
A = [Al(OC(CF3)2CH2SiMe3)4]
(Eq C-4)ndashLiCl
Compound C-3 is at least stable for several days at room temperature in CD2Cl2 solution but
decomposes after storage for several days at 333 K Visually it can be detected by color
change from yellow to dark brown
38
Table C-1 1H 13C and 27Al NMR data of crystalline C-1 C-2 compared to the data from the NMR scale
syntheses to [Ph3C]+[Al(OC(CF3)2CH2SiMe3]ndash (cf Eq C-4) for X = Cl (C-3) BF4 (C-4) taken in CD2Cl2 at
298 K
Nucleus Chemical shift Chemical shift Chemical shift Assignment δ [ppm] (C-1) δ [ppm] (C-2) δ [ppm] (C-3) 1H 001 s1) 002 sa) 001 sb) ndash(CH3)3 111 s1) 148 sa) 156 sb) ndashCH2 - - 775 db) ndashCH (ring o) - - 3JHH = 678 Hz - - 791 tb) ndashCH (ring m) - - 3JHH = 678 Hz - - 829 tb) ndashCH (ring p) - - 3JHH = 678 Hz 13C[1H] 000 s 013 s 000 s ndash(CH3)3 259 t 247 t 259 t ndashCH2 784 sept 785 sept 789 sept broad ndashC(CF3)2 2JCF = 31 Hz 2JCF = 32 Hz 2JCF = 325 Hz 1263 q 1249 q 1231 q ndashC(CF3)2 1JCF = 275 Hz 1JCF = 276 Hz 1JCF = 279 Hz - - 1322 s ndashCH (ring m) - - 1400 s ndashC (ring ipso) - - 1416 s ndashCH (ring p) - - 1439 s ndashCH (ring o) - - 2117 s ndashCPh3 19F ndash760 s ndash758 ndash756 s 27Al - 463 s 459 s AlndashOC - ∆12 = 1130 Hz ∆12 = 1110 Hz 7Li ndash04 s ndash05 s - a)250 MHz-1H NMR b)400 MHz-1H NMR
The 1H and 13C NMR data of C-1 and C-2 show typical chemical shifts the quaternary carbon
atom can be found at 785 ppm and the carbon atoms of the CF3 groups are similar to those of
the known fluorinated alkoxy aluminates[5] 1H and 13C NMR shifts and coupling constants of
C-3 are as expected for the trityl cation [Ph3C]+ and the intact anion After storage at 333 K
for several days compound C-3 decomposes (NMR) The CndashF coupling constants of C-1 and
C-2 are in good agreement with the literature[5] The 27Al signal at 46 ppm (∆12 = 1130 Hz) is
comparable to the normal aluminum shifts in the known fluorinated aluminate Li+[Al(ORF)4]ndash
(RF = C(H)(CF3)2)[5] Vibrational spectra (IR and Raman) of C-2 are as expected and a
39
complete table in which the bands are compared to Li+[Al(ORF)4]ndash (RF = C(CH3)(CF3)2)[5] is
deposited in Chapter J
C11 Attempted further synthesis
of [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4)
The reaction of C-2 with HCl(g) and Et2O was carried out to investigate the stability of the
new WCA towards cationic proton acids However the attempted synthesis to the [H(OEt2)2]+
complex failed Moreover the resulting residue was identified by mass balance and NMR to
be the decomposition product Al[OC(CF3)2(CH2)Si(CH3)3]3 together with LiCl probably
formed by Eq C-5
Li+[Al(ORF)4]ndash (C-2) + HCl + 2Et2O [H(OEt2)2]+[Al(ORF)4]ndash (C-4) + LiCl
Al(ORF)3 + LiCl + 2Et2O + RFOH
RF = C(CF3)2(CH2)SiMe3 (Eq C-5)
CH2Cl2
The mass of the precipitate (m = 059 g 92 ) fits very well to theoretical yield for both non
volatile components (Al(ORF)3 and LiCl) of 064 g (100 ) The theoretical yield for the
proposed product [H(OEt2)2]+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-4) should be 091 g NMR
measurements of the residue are in agreement with this proposal Thus the alkoxy aluminate
C-2 is not stable in the presence of strong acids like [H(OEt2)2]+
C2 Crystal Structure
Yellowish block shaped single crystals of C-2 are monoclinic space group P21c (Z = 8) The
solid state structure consists of a 1D polymer of (Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash)n (n = infin)
The seven coordinate Li(2)+-cation binds a [Al(OC(CF3)2(CH2SiMe3)]ndash-anion that serves as
40
hexadentate O2F4 ligand (see Fig C-2 right) and accepts one further intermolecular
coordination to the peripheral F(18) atom from a second anion Drawings of the extended
solid state structure are deposited in Chapter J
O13
O13
Fig C-2 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) at 150 K with
thermal displacement ellipsoids showing 50 probability F(18) stems from the CF3 groups of a second anion
in the lattice The H atoms are described as balls with a reduced radius of 01 Aring A section of one of the seven
coordinated Li cations is given on the right The most important atom labels are given in the figure bond lengths
are given in [Ǻ] and angles in [deg] (cf also Table C-2) Li(1)ndashO(1) 1973(10) Li(1)ndashO(14) 1973(10) O(1)ndash
C(101) 1400(6) O(4)ndashC(122) 1393(7) O(12)ndashC(108) 1382(7) O(13)ndashC(115) 1408(6) Oslash(C-C) 1527 Oslash(Cndash
F) 1339(3) Oslash(SindashC) 1862(5)
The LindashO coordination is found at 1950 Aring and 1945 Aring as a distorted tetrahedral and the
planar four membered (LindashOndashAlndashO) ring includes an AlndashOndashLi angle of 970deg which is
widened about 27deg in comparison to the [Al(OC(H)(CF3)2)4]2ndash-anion in
[Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash (699deg)[6] The coordination environment of the Li+ cation is
further saturated by four weak intramolecular LihellipF contacts at 2413 to 2789 Aring (average
2535 Aring) and the intermolecular distance to the fifth F(18) atom is short at 2042 Aring giving an
unusual sevenfold coordination environment of Li+
41
In gaseous LiF d(LiF) is 1564 Aring[7] while it is 2001 Aring in the [LiF]n solid state[8] hence only
four hundredthsrsquo of an angstrom shorter than Li(2)hellipF(18) The LihellipF distances for the
compound [(CMe3)2SiFLiNCMe3]2[9] from 1851 to 2087 Aring gave rise to a 1JLiF NMR
coupling of 33 Hz in solution However in this case LindashF coupling was absent Compared to
the dimeric structure in [Ph3C]+[Li[Al(OC(H)(CF3)2)4]2]ndash[6] the range of the LindashF distances
(2710 to 2928 Aring) is shortened by about 0383 Aring (av) (cf Table C-1) The four LindashF bonds
within the [Al(OC(CF3)2CH2SiMe3)4]ndash-anion (C-2) although clearly weaker than the two Lindash
O bonds are still significant as they are needed so that the sum of the lithium bond valences
(included in Table C-2) reaches nearly unity (found 0882 (Li+[Al(OC(Ph)(CF3)2)4]ndash[1] ΣLi
1041 Li+[Al(OC(H)(CF3)2)4]ndash[4] ΣLi 0786))[4 10 11] The sum of the bond valances in C-2
underlines the unsaturated bulky environment of Li The [Al(OC(CF3)2CH2SiMe3)4]ndash-anion
exhibits one set of AlndashO distances and AlndashOndashC bond angles to di-coordinated oxygen atoms
at 1712 Aring 1714 Aring 1429deg and 1407deg as well as a set of AlndashO distances and AlndashOndashC bond
angles to tri-coordinated oxygen atoms at 1771 Aring 1759 Aring 1353deg and 1418deg The short
AlndashO bonds are in a range as earlier observed for tricoordinated Al(OAryl)3 compounds and
suggested together with the wide AlndashOndashC bond angles a rather ionic nature of the AlndashO bonds
in the tetra-coordinated [Al(ORF)4]ndash anions Other structural parameters of the anion in C-2
are also in good agreement to the ones observed in the literature[1 4 6] and are compared in
Table C-2
42
Table C-2 Comparison between related bond lengths [Aring] and angles [deg] of compound C-2
Li+[Al(OC(Ph)(CF3)2)4]ndash[1] and Li+[Al(OC(H)(CF3)2)4]ndasha)[4]
bond distance C-2 Li+[Al(OC(Ph)(CF3)2)4]ndash Li+[Al(OC(H)(CF3)2)4]ndash
d(LindashOtri) 1950(1) [0270] 1978(8) [0251] 2089(5) [0186] 1945(10) [0274] 1966(8) [0259] 2016(5) [0226] - - 2166(6) [0151] d(LindashOtetra) - - 2533(6) [0056] d(AlndashOtri) 1771(3) [0665] 1773(2) [0661] 1758(2) [0689] 1759(4) [0687] 1755(3) [0694] 1766(2) [0674] d(AlndashOdi) 1715(4) [0774] 1706(3) [0793] 1690(2) [0828] 1711(4) [0782] 1687(3) [0834] 1771(2)b) [0665] d(LindashF) 2042(10) [0158] 1984(9) [0185] 2366(6) [0066] 2413(10) [0058] 2082(9) [0142] 2414(6) [0058] 2463(11) [0051] 2098(11) [0136] 2798(6) [0021] 2466(10) [0050] 2354(10) [0068] 3055(6) [0010] 2789(9) [0021] - 3181(6) [0007] - - 3327(6) [0005] lt(LindashOndashAl) 970(3) 946(2) 964(2) 979(3) 936(2) 934(2)b) lt(OtrindashLindashOtri) 776(4) 799(3) 750(1)b) lt(OtrindashAlndashOtri) 875(16) 918(1) 945(2)b) lt(OdindashAlndashOdi) 10910(19) 1054(1) 1121(4)c) lt(OtrindashAlndashOdi) 1172(2) 1125(1) 981(8)b) 1160(2) 1148(1) 1110(4)c) 11341(19) 1158(1) 1124(2)c) 11236(19) 1167(1) 1270(6)b)
a)The centrosymmetric [LiAl(OC(H)(CF3)2)4]2 dimer b)Otetra tetra-coordinated O-atoms c)Otri tri-coordinated O-atoms
C3 Conclusion
The lithium alkoxy aluminate Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (C-2) represents a new
weakly coordinating anion that may also be prepared in a one pot reaction The bulk of the
ndashCH2ndashSi(CH3)3 group shields the oxygen atoms and induces solubility in aliphatic solvents
like n-hexane The salt is apparently soluble in polar and non-polar solvents This confirms
that C-2 shoud be an excellent candidate for Li ion catalysis and for the coordination
chemistry of Li+ with weak ligands Its [Ph3C]+-salt is accessible and stable in solution over
days However attempts to prepare the cationic BrOslashnsted acid [H(OEt2)2]+ only led to anion
decomposition
43
References to Chapter C
[1] T J Barbarich S T Handy S M Miller O P Anderson P A Grieco S H Strauss Organometallics 1996 15 3776
[2] J J Rockwell G M Kloster W J DuBay P A Grieco D F Shriver S H Strauss Inorg Chim Acta 1997 263 195
[3] S Moss B T King A de Meijere S I Kozhushkov P E Eaton J Michl Org Lett 2001 3 2375 [4] S M Ivanova B G Nolan Y Kobayashi S M Miller O P Anderson S H Strauss Chem Eur J
2001 7 503 [5] I Krossing ChemEur J 2001 7 490 [6] I Krossing H Brands R Feuerhake S Koenig J Fluorine Chem 2001 112 83 [7] D R Lide CRC Handbook of Chemistry and Physics 1995-1996 76th Ed [8] I L Shamovskii L M Shamovskii A I Boldyrev V V Nefedova Russ Chem Bull 1989 38 10 [9] D Stalke U Klingebiel G M Sheldrick J Organomet Chem 1988 344 37 [10] I D Brown D Altermatt Acta Crystallogr B Struct Sci 1985 B41 244 [11] J A Samuels E B Lobkovsky W E Streib K Folting J C Huffman J W Zwanziger K G
Caulton J Am Chem Soc 1993 115 5093
44
D A Simple Access to the Non-Oxidizing Lewis Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Much recent work has been dedicated to the design of very strong molecular Lewis acids
which are commonly used in rearrangement reactions catalysis ionization- and bond
heterolysis reactions[1-5] Several schemes to evaluate the strengths of a Lewis acid were
developed[3 4 6] However it is known since the pioneering work of N Bartlett et al[7] that the
fluoride ion affinity (FIA) is as a reliable measure for the Lewis acidity of A(g) with respect to
the fluoride ion (Eq D-1)[7-9]
)g(AFFIAHFA )g()g(minusminus ⎯⎯⎯⎯⎯ rarr⎯ minus=∆+ (Eq D-1)
The enthalpy ∆H (Eq D-1) corresponds the negative of the FIA and the higher the FIA value
the stronger is the Lewis acid From recent work it became evident[9] that Lewis acids stronger
than SbF5 are now available as compounds in the bottle eg As(OTeF5)5[10 11] B(OTeF5)3[12]
F4C6(B(C6F5)2)2[13] and others (Table D-1) To account for the special properties of these very
strong Lewis acids it appears reasonable and useful to define the term ldquoLewis Superacidrdquo[14]
ldquoMolecular Lewis acids which are stronger (ie have a higher FIA) than monomeric SbF5 in
the gas phase are Lewis Superacidsrdquo
This definition may be seen in analogy to Broslashnsted acids Broslashnsted Superacids are stronger
than the strongest conventional Broslashnsted acid 100 H2SO4[15] Since SbF5 is commonly
viewed as the strongest conventional Lewis acid this definition appears only logic Let us
now turn to the measure for Lewis acidity the FIA it can be assessed by several means[7-9 16]
However the simplest and most general access to reliable FIA values now comprises the use
45
of quantum chemical calculations in an isodesmic reaction[8] Table D-1 shows the calculated
FIAs of a representative set of strong neutral Lewis acids[9]
Table D-1 Representative overview to known strong Lewis acids and their corresponding fluoride
complexes[17 18] Unstable and hitherto unknown Lewis acids that were only accessible on computational
grounds are shown in italics (stability refers to standard conditions 298 K 1013 mbar) the dashed line marks
the border between normal and Lewis Superacids If not otherwise stated FIA values are taken from reference[9]
or were calculated as part of this work using the same methodology as in[9]
Lewis acidanion FIA [kJ mol-1][9] Lewis acidanion FIA
[kJ molndash1][9]
Sb(OTeF5)5[19][FSb(OTeF5)5]ndash 633 AlCl3
b)[FAlCl3]ndash 457 [332]c)
[this work] As(OTeF5)5
[10 11][FAs(OTeF5)5]ndash[20] 593 GaI3b)[FGaI3]ndash 454[this work]
AuF5[21 22][AuF6]ndash[21 22] 556[23] BI3[FBI3]ndash 448[this work]
B(CF3)3[FB(CF3)3]ndash[24] 552 B(C12F9)3[25 26]
[FB(C12F9)3]ndashe) 447[this work]
B(OTeF5)3[12][FB(OTeF5)3]ndash 550 Ga(C6F5)3[FGa(C6F5)3]ndash 447[this work]
Al(ORF)3[FAl(ORF)3]ndasha) 537 B(C6F5)3[27][FB(C6F5)3]ndash[28] 444
Al(C6F5)3[29 30][FAl(C6F5)3]ndash[31] 530[this work] GaBr3
b)[FGaBr3]ndash 436[this work] F4C6(12ndash(B(C6F5)2)2)2
[13] [F4C6(12ndash(B(C6F5)2)2)F]ndashe) 510 BBr3[FBBr3]ndash 433[this work]
PhndashFrarrAl(ORF)3[FAl(ORF)3]ndash + PhndashFa) 505[this work] GaCl3b)[FGaCl3]ndash 432[this work]
AlI3b)[FAlI3]ndash 499 [393]c)[this work] GaF3
b)[FGaF3]ndash 431[this work AlBr3
b)[FAlBr3]ndash 494 [393]c)[this work] AsF5[AsF6]ndash 426 SbF5[SbF6]ndash 489 [434]c) BCl3[FBCl3]ndash 405[this work]
B2(C6F5)(C6F4)2[32][FB2(C6F5)(C6F4)2]ndashe) 471 OCndashB(CF3)3[FB(CF3)3]ndash + COc) 404[this work]
B(C6H3(CF3)2)3[FB(C6H3(CF3)2)3]ndash[33] 471 PF5[PF6]ndash 394 B(C10F7)3
[25][FB(C10F7)3]ndash[34]e) 469[this work] BF3[BF4]ndash 338 AlF3
b)[FAlF3]ndash 467 a)RF = C(CF3)3 b)monomeric EX3 (E = Al Ga) c)Values in brackets are with respect to the standard state of the Lewis acid ie solid for AlX3
[35] and liquid for SbF5[36] d)However OCndashB(CF3)3 reacts with Fndash by formation of [F(O)CndashB(CF3)3]ndash[37] e)Molecular structures F4C6(12-(B(C6F5)2)2)2
FF
B
BF
F
FF
B
BF
FF
C6F5 F
F
FF
3
FF B
BF
F
FF
FF
FF
BF
FF
FF 3
B(C12F9)3 B(C10F7)3[F4C6(12-(B(C6F5)2)2)2F]-
C6F5
C6F5
B
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
C6F5
B2(C6F5)2(C6F4)2
Inspection of Table D-1 shows that according to its FIA value and apart from monomeric
AlBr3 and AlI3 SbF5 is the strongest conventional ie easily accessible under normal
conditions stable and in technical applications employed[38] Lewis acid However solid liquid
and gaseous AlX3 shows a strong tendency towards aggregation which diminishes the Lewis
46
acidity more effectively than the aggregation in SbF5 (see values in brackets) Thus the basis
for our definition above is reasonable Lewis Superacids like AuF5[22] or As(OTeF5)5
[10 11] are
stronger than SbF5 but are elusive entities that are scarcely used if at all Further entries like
B(CF3)3[39 40] or Sb(OTeF5)5
[19] are only available on computational grounds but not as a
compound in the bottle None of the Lewis Superacids collected in Table D-1 is accessible in
bulk quantities and is used in commercial applications Al(C6F5)3 even has a reputation of
being explosive[29 30 41] It is likely that the amorphous Lewis acids ACF (AlClxF3-x x = 005 -
03) and ABF (AlBrxF3-x x = 013) present an exception[42] however these extended solid
state compounds are impossible to compare to molecular Lewis acids as collected in Table
D-1 and thus are not considered Moreover all of the very strong Lewis acids collected in
Table D-1 have drawbacks in that they are either highly oxidizing (AsF5 SbF5 M(OTeF5)5
etc) andor often easily hydrolyze with formation of anhydrous HF (aHF) This does not hold
for the organometallic boron acids B(ArF)3 (ArF = C6F5 etc) however apart from the
chelating F4C6(12ndash(B(C6F5)2)2)2 those are all weaker and no Lewis Superacids Thus a
simple access to a non oxidizing Lewis Superacid that does not hydrolyze with formation of
hazardous chemicals like aHF would be desirable Herein we report on a simple and straight
forward synthesis of a compound that we classify on experimental and theoretical grounds as
a non oxidizing Lewis Superacid
The FIAs of small gaseous aluminum Lewis acids like monomeric AlX3 (X = F Cl Br I FIA
= 457 to 499 kJ molndash1)[9] are close to or even higher than that of monomeric SbF5
(489 kJ molndash1)[9] Table D-1 shows that the replacement of monoatomic ligands like F by
electronegative polyatomic ligands like OTeF5 CF3 or C6F5 leads to a large increase in Lewis
acidity Thus it appeared reasonable to postulate that an aluminum Lewis acid bearing the
bulky perfluorinated alkoxy ligand ORF (RF = C(CF3)3) - that prevents the alanes from
dimerization - should be a stronger acid than the parent AlX3 compounds This was verified
47
by quantum chemical calculations that gave the FIA of Al(ORF)3 as 537 kJ molndash1[9] and which
is in agreement with the assignment as a Lewis Superacid Thus the preparation of Al(ORF)3
from AlR3 (R = Me Et) according to equation D-2 was attempted
AlR3 + RFOH273K ndash3RH
Al(ORF)3Solvent
(Eq D-2)
Indeed aluminumtrialkyls react by solvolysis with the perfluorinated alcohol and form the
Lewis Superacid Al(ORF)3 with quantitative formation of RH (measured) However in
toluene impure and brown colored products which also contain a larger degree of unassigned
decomposition products were obtained If prepared in CH2Cl2 Al(ORF)3 is soluble but tends
to internal (C)ndashF abstraction and formation of decomposed products with AlndashFndashAl bridges at
273 K again in agreement with Al(ORF)3 being a Lewis Superacid Aliphatic solvents are
suited for the synthesis but the colorless precipitate of Al(ORF)3 is insoluble in those solvents
and Al(ORF)3 decomposes above 273 K At 273 K the pentanehexane suspension may be
used in situ for further reactions (=gt preparation of [FAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash salts cf Chapter E)[43] Isolation of solid Al(ORF)3 at ambient
conditions was very difficult because of decomposition with CndashF activation and formation of
fluoroaluminates Some insight for the reasons of the CndashF activation comes from the DFT
optimized structure of Al(ORF)3[9] Due to the high Lewis acidity of the tricoordinate
aluminum atom it also binds two fluorine atoms of the CF3 groups at 213 Aring (av Fig D-1)
48
O1O2
O3
AlF F
C1
C3
C2
2143Aring 2115Aring
Fig D-1 DFT optimized structure of Al(ORF)3 (RF = C(CF3)3) at the BP86SV(P) level
shown as ball-and-stick model
We interpret this as the first step towards CndashF bond cleavage and decomposition To avoid the
easy ambient temperature decomposition of Al(ORF)3 an alternative has been developed to
stabilize this Lewis superacid and to provide an easily accessible room temperature stable
reagent that may widely be used in all applications that need high and hard Lewis acidity
internal coordination of the weak Lewis base PhndashF Thus if reaction (Eq D-2) is performed
in fluorobenzene the adduct PhndashFrarrAl(ORF)3 D-1 forms in 98 isolated crystalline yield
The compound is highly soluble in PhndashF at 273 K (PhndashF stock solutions with concentrations
up to 828 g Lndash1 (= 10 mol Lndash1) were prepared) A PhndashF solution of D-1 is in contrast to free
Al(ORF)3 stable for days at rt Large single crystals of PhndashFrarrAl(ORF)3 form upon cooling
to 253 K may be isolated and are stable for weeks at 273 K but may also be handled at rt in
the atmosphere of a glove box (for at least an hour) The 19F NMR spectrum of
PhndashFrarrAl(ORF)3 in C6D5F shows the typical singlet of the equivalent CF3 groups at δ19F =
ndash752 ppm At ndash1440 ppm the signal of the coordinated PhndashFrarrAl is found (calc
ndash1386 ppm BP86SV(P)) In the 19F NMR spectrum the signals of deuterated and
nondeuterated PhndashF are visible and suggest facile exchange on the time scale of NMR The
27Al spectrum of D-1 shows one broad signal at 38 ppm (∆12 = 2350 Hz) and the IR spectrum
49
the expected bands that were completely assigned based on the calculated IR spectrum
(deposited in Chapter J) The crystal structure of D-1 is shown in Fig D-2
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig D-2 Molecular structure of [PhndashFrarrAl(ORF)3] (D-1) (RF = C(CF3)3) at 100 K with thermal displacement
ellipsoids showing 50 probability Selected bond lengths are given in [Aring] and angles in [deg] Al(1)ndashO(3)
1685(2) Al(1)ndashO(2) 1693(2) Al(1)ndashO(1) 1706(2) Al(1)ndashF(1) 1864(2) Al(1)ndashF(2) 2770(8) O(1)ndashC(7)
1369(3) O(2)ndashC(11) 1365(3) O(3)ndashC(15) 1364(3) F(1)ndashC(1) 1447(3) O(3)ndashAl(1)ndashO(2) 11583 (10) O(3)ndash
Al(1)ndash(O1) 12143(10) O(2)ndashAl(1)ndashO(1) 11322(10) O(3)ndashAl(1)ndashF(1) 10283(9) O(2)ndashAl(1)ndashF(1) 10301
O(1)ndashAl(1)ndashF(1) 9530(9) C(7)ndashO(1)ndashAl(1) 13808(18) C(11)ndashO(2)ndashAl(1) 15016(19) C(15)ndashO(3)ndashAl(1)
15156(19) C(1)ndashF(1)ndashAl(1) 12999(15)
The core of this molecule consists of a quite distorted FAlO3 tetrahedron (Σ(OndashAlndashO) =
3505deg cf 3285deg for an ideal tetrahedron) The three AlndashO bonds are at 1695 Aring (av) and
the coordinative AllarrFndashPh bond at 1864(2) Aring (Fig D-2 calculated (BP86SV(P)) d(Alndash
O)av 1728 d(AlndashF) 1975 Aring) Compared to the homoleptic [Al(ORF)4]ndash[44] anion the AlndashORF
bonds are further shortened by about 003 Aring while the average AlndashOndashC bond angle of 1509deg
of the two free (Alndash)ORF groups is almost unchanged[45] The Al(1)ndashF(1) bond of 186 Aring is
relatively long and may be compared to benchmark compounds like [CPh3]+[FndashAl(ORF)3]ndash[46]
with a clear bond order of 1 and an AlndashF distance of 166 Aring as well as to the fluoride bridged
[(RFO)3AlndashFndashAl(ORF)3]ndash anion with a clear bond order of 05 and an AlndashF distance of about
50
177 Aring (several salts[47 48]) This is in agreement with the observed weak PhndashF coordination in
solution (exchange with FndashC6D5) Although the C(CF3)3 ligand is rather bulky all AlndashO
distances are very short and indicate an electron deficient highly acidic aluminum center in D-
1 According to a CSD search D-1 comprises the first neutral Lewis acid that coordinates the
weak nucleophile PhndashF via the F-atom The only available example of a fluorine bound PhndashF
complex is cationic [(η5ndashC5H5)2TilarrFndashPh]+[49] Although the adduct D-1 is weak there is a
noticeable influence on the complexed C(1)ndashF(1) bond that is elongated by 006 Aring with
respect to free fluorobenzene at 136 Aring This might be useful for transformations of the PhndashF
moiety (coupling reactionshellip)
To verify the weakness of the PhndashF coordination to Al(ORF)3 the complexation enthalpy has
been calculated (BP86SV(P)) ∆rHdeggas (Eq D-3) is ndash32 kJ molndash1 and slightly favors
coordination of PhndashF by the Lewis acid however entropy is against coordination and in
agreement with this the Gibbs complexation energy in the gas phase is slightly unfavorable
both in the gas phase (∆rGdeggas (Eq D-3) = +8 kJ molndash1) and in PhndashF solution (∆rGdegsolv (Eq D-
3) = +9 kJ mol-1 COSMO solvation εr = 5841)[50] In PhndashF solution at 257 K we have shown
that dynamic exchange between deuterated and non deuterated PhndashF occurs ie the
coordination of PhndashF is reversible and provides access to free Al(ORF)3 in solution Further
experiments showed that the Lewis Superacid D-1 is stable in PhndashF but decomposes in
CH2Cl2 at 298 K An analysis of equilibrium (Eq D-3) shows how the stability of D-1 is
depending on the [PhndashF] concentration
PhndashF + Al(ORF)3
[PhndashF][Al(ORF)3]K =
D5ndashPh-FPhndashF Al(ORF)3 (Eq D-3)
PhndashF Al(ORF)3
51
In CH2Cl2 the concentration of [PhndashF] is equal to that of free Al(ORF)3 and large enough to
allow decomposition of the free Lewis acid by CndashF activation (see Fig D-1 and above) In
PhndashF solution the concentration of [PhndashF] is much larger since it is used as a solvent Thus
to keep K constant the Al(ORF)3 concentration has to be very small and thus
PhndashFrarrAl(ORF)3 is stable in this solvent over days at rt From the equilibrium (Eq D-3) and
its solvent dependence may also be followed that that ∆Gdegsolv must be close to 0 kJ molndash1
(K asymp 001-100) This conclusion is supported by the BP86SV(P) calculated value for ∆rGdegsolv
of 9 kJ molndash1 which would give Kcalc as 003
To further experimentally support the superacidity of PhndashFrarrAl(ORF)3 (cf Table D-1) the
reaction of D-1 with a suitable source of [SbF6]ndash eg the ionic liquid [BMIM]+[SbF6]ndash was
performed Eq D-4 proceeded successfully with fluoride abstraction from [SbF6]ndash by the
Lewis acid PhndashFrarrAl(ORF)3
+ 2[SbF6]ndash() [FAl(ORF)3]ndash
ndash1PhF+ PhndashF Al(ORF)3
[(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
+ [Sb2F11]ndash
fast furtherreaction∆solvGdeg = ndash177 kJ molndash1
gasGdeg = ndash299 kJ molndash1
gasHdeg = ndash300 kJ molndash1∆∆
()from [BMIM]+[SbF6]ndash
in PhF
ndash2 PhndashF
ndash1PhndashF
2PhndashF Al(ORF)3
(Eq D-4)
The formation of the [FAl(ORF)3]ndash-anion indicates the fluoride abstraction of the [SbF6]ndash
anion however the intermediately generated Lewis acid SbF5 further reacts with another
[SbF6]ndash anion to form [Sb2F11]ndash[51] which was reproducibly assigned in the NMR spectra of
several reactions (NMR scale and batch reactions) δ19F([Sb2F11]ndash) = ndash999 ndash1157 ndash1336
[ppm] Lit[52] δ19F = ndash904 ndash1167 ndash1387 [ppm] Similarly to SbF5 the Lewis acid Phndash
52
FrarrAl(ORF)3 reacts further with the fluoride complex [FAl(ORF)3]ndash giving the fluoride
bridged anion (NMR X-ray structure of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash[53]) The course of
reaction in equation D-4 is in agreement with calculations at the BP86SV(P) level where the
first half of the reaction is exergonic by ∆solvGdeg = ndash102 kJ molndash1 and the entire reaction (Eq
D-4) by ∆solvGdeg = ndash177 kJ molndash1
D1 Conclusion
In this thesis Lewis Superacids are defined as compounds with a higher Lewis acidity (FIA)
than the strongest conventional and commercially employed Lewis acid SbF5 (FIA = 489 kJ
molndash1) The nonoxidizing Al(ORF)3 has a FIA of 537 kJ molndash1 and thus qualifies as a Lewis
Superacid however is not very stable at ambient conditions By weak coordination of PhndashF
the Lewis acid is greatly stabilized stable at rt highly soluble in PhndashF and easily accessible
in a quantitative yield one step procedure starting from commercially available materials The
FIA of PhndashFrarrAl(ORF)3 is 505 kJ molndash1[54] ie higher than that of gaseous SbF5 and further
enhanced by entropy (liberation of PhndashF) The Lewis superacidity of PhndashFrarrAl(ORF)3 (D-1)
was experimentally proven by reaction with an [SbF6]ndash salt ([Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash formation) Thus it is anticipated that the non oxidizing Lewis
Superacid PhndashFrarrAl(ORF)3 may find wide spread applications in all areas where maximum
hard Lewis acidity is needed but oxidative conditions are not tolerated
53
References to Chapter D
[1] E Y-X Chen T J Marks Chem Rev 2000 100 1391 [2] M H Valkenberg C de Castro W F Hoelderich Stud Surf Sc Cat 2001 135 4629 [3] A Corma H Garcia Chem Rev 2002 102 3837 [4] A Corma H Garcia Chem Rev 2003 103 4307 [5] H Li T J Marks Proc Natl Acad Sci Chem 2006 103 15295 [6] A Haaland Angew Chem 1989 101 1017 [7] T E Mallouk G L Rosenthal G Mueller R Brusasco N Bartlett Inorg Chem 1984 23 3167 [8] K O Christe D A Dixon D McLemore W W Wilson J A Sheehy J A Boatz J Fluorine Chem
2000 101 151 [9] I Krossing I Raabe Chem Eur J 2004 10 5017 [10] M J Collins G J Schrobilgen Inorg Chem 1985 24 2608 [11] D Lentz K Seppelt ZAAC 1983 502 83 [12] F Sladky H Kropshofer O Leitzke J Chem Soc Chem Comm 1973 134 [13] V C Williams W E Piers W Clegg M R J Elsegood S Collins T B Marder
J Am Chem Soc 1999 121 3244 [14] The term ldquoLewis Superacid was occasionally usedrdquo[11 26] However no solid definition of this term has
been given [15] R J Gillespie Canad Chem Ed 1969 4 9 [16] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [17] (Me3SindashC(C6F5)(Ntf2)2) that was addressed as Lewis Superacid is difficult to compare since it reacts
with Fndash to Me3SiF and [C(C6F5)(Ntf2)2]ndash With respect to the latter reaction its FIA is 635 kJ molndash1 however it appears not wise to include the compound in Table D-1
[18] A Hasegawa K Ishihara H Yamamoto Angew Chem Int Ed 2003 42 5731 [19] H P A Mercier J C P Sanders G J Schrobilgen J Am Chem Soc 1994 116 2921 [20] M Gerken P Kolb A Wegner H P A Mercier H Borrmann D A Dixon G J Schrobilgen Inorg
Chem 2000 39 2813 [21] V B Sokolov V N Prusakov A V Ryzhkov Y V Drobyshevskii S S Khoroshev Dokl Akad
Nauk 1976 229 884 [22] I-C Hwang K Seppelt Angew Chem Int Ed 2001 40 3690 I-C Hwang K Seppelt Angew Chem 2001 113 3803 [23] L Muumlller calculation at the BP86SV(P) level to compare the calculated FIAs of the Lewis acids under
the same conditions See also for AuF5 Structure and Fluoride Affinity I-C- Hwang K Seppelt Angew Chem 2001 113 and Angew Chem Int Ed Engl 2001 40
[24] E Bernhardt M Finze H Willner C W Lehmann F Aubke Angew Chem Int Ed 2003 42 2077 [25] L Li T J Marks Organometallics 1998 17 3996 [26] Y-X Chen C L Stern S Yang T J Marks J Am Chem Soc 1996 118 12451 [27] A G Massey A J Park J Organomet Chem 1964 2 245 [28] D Naumann W Tyrra J Chem Soc Chem Comm 1989 47 [29] J Klosin G R Roof E Y X Chen K A Abboud Organometallics 2000 19 4684 [30] T Belgardt J Storre H W Roesky M Noltemeyer H-G Schmidt Inorg Chem 1995 34 3821 [31] M-C Chen J A S Roberts A M Seyam L Li C Zuccaccia N G Stahl T J Marks Organomet
2006 25 2833 [32] M V Metz D J Schwartz C L Stern T J Marks P N Nickias Organometallics
2002 21 4159 [33] K Fujiki S-Y Ikeda H Kobayashi A Mori A Nagira J Nie T Sonoda Y Yagupolskii Chem
Lett 2000 62 [34] M-C Chen J A S Roberts T J Marks Organometallics 2004 23 932 [35] The procedure for solid AlX3 is deposited in Chapter J [36] H D B Jenkins I Krossing J Passmore I Raabe J Fluorine Chem 2004 125 1585 [37] M Finze E Bernhardt H Willner C W Lehmann Angew Chem Int Ed 2003 42 1052 M Finze E Bernhardt H Willner C W Lehmann Angew Chem 2003 115 1082 [38] V M Allenger P S Yarlagadda R N Pandey Erdoel amp Kohle Erdgas Petrochemie 1991 44 244 [39] However the CO adduct OCndashB(CF3)3 may serve as a (weaker) equivalent to free B(CF3)3 [40] M Finze E Bernhardt M Zaehres H Willner Inorg Chem 2004 43 490 [41] N G Stahl M R Salata T J Marks J Am Chem Soc 2005 127 10898 [42] T Krahl E Kemnitz Angew Chem Int Ed 2004 43 6653 T Krahl E Kemnitz Angew Chem 2004 116 6822
54
[43] I Krossing M Gonsior L Mueller WO 2004-EP12220 2005054254 (Universitaumlt Karlsruhe TH Germany) 2005
[44] I Krossing Chem Eur J 2001 7 490 [45] However due to a weak internal Al(1)ndashF(2) interaction (2778 Aring) one of the ORF-ligands adopts a
smaller AlndashOndashC angle of 1381deg [46] to be published [47] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [48] M Gonsior L Mueller I Krossing Chem Eur J 2006 12 5815 [49] M W Bouwkamp P H M Budzelaar J Gercama I D H Morales J de Wolf A Meetsma S I
Troyanov J H Teuben B Hessen J Am Chem Soc 2005 127 14310 [50] A Klamt G Schuumluumlrmann J Chem Soc 1993 799 [51] This assignment is further supported by an reaction of SbF5 with PhndashF Liquid SbF5 was added to liquid
PhndashF at rt in a glove box an oxidation occurs and the solution turns intensely green In the reactions according to Eq D-4 we never observed the green coloration This suggests that the fluoride ion is removed from [SbF6]ndash in an associative process eg [(RFO)3AlndashFhellipSbF5hellipSbF6]2ndash rarr [(RFO)3AlndashFndashAl(ORF)3]ndash + [Sb2F11]ndash
[52] J-C Culmann M Fauconet R Jost J Sommer New J Chem 1999 23 863 [53] Unfortunately the quality of the structure is not good due to twinning and disorder Some details of the
refinement are given Space group P1 cell constant 113443 Aring 113787 Aring 128865 Aring 109202deg 97371deg 118639deg R1 = 261 39402 reflections completeness 98 2θ 28deg 11493 data 852 parameters
[54] L Muumlller unpublished results 2007 [55] D Himmel I Krossing unpublished results 2006
55
E The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated
fluorinated anion [FAl(ORF)3]ndash (RF = C(CF3)3)
As mentioned in Chapter D the compounds Al(ORF)3 (FIA 537 kJ molndash1) and its
corresponding adduct complex PhndashFrarrAl(ORF)3 (FIA 505 kJ molndash1) are Lewis Superacids
Superacids or Broslashnstedt Superacids (those stronger than 100 sulfuric acid)[1] have been of
great value to chemistry superacidity has been used to stabilize carbenium carbonium[2] and
other elemental onium ions[3] as well as to study acid-catalyzed processes[4] While the tert-
butyl cation is readily stabilized in classical superacid media and can be isolated as
[Me3C]+[Sb2F11]ndash[5] the corresponding silyl chemistry leads to species having covalent bonds
to oxy or fluoro anions eg [SbF6]ndash is too nucleophilic to stabilize a free [R3Si]+ silylium ion
and decomposes giving R3SiF and SbF5[6] (R = eg Me) By contrast the known R3SiX
compounds lie along a continuum between idealized sp3 and sp2 geometries ie an admixture
of covalent and ionic This ion-like[6] character of a [R3Si]+[X]ndash is already known in
compounds like i-Pr3Si(CB11H6Cl6) and others[7] The long search for a free silylium ion was
only recently met by success[8] In inorganic chemistry the oxidizing nature of classical
superacids has been widely exploited to stabilize unusual reactive cations such as [S8]2+
[Ir(CO)6]3+ [Xe2]+[9-11] and [Xe4]+[12]
The combination of oxidizing capacity together with Lewis acidity make classical Lewis and
Broslashnsted Superacids corrosive destructive and limit their academic and industrial application
By contrast the Lewis Superacid Al(ORF)3 is non oxidizing and reacts under fluoride ion
abstraction with [SbF6]ndash giving first [FAl(ORF)3]ndash and then [Sb2F11]ndash and
[(RFO)3AlndashFndashAl(ORF)3]ndash[13] The further motivation was the use of the Al(ORF)3 Lewis
Superacid in reactions with fluorinated compounds ie Me3SiF [NBu4]+[BF4]ndash and
56
Ag+[BF4]ndash yielding the ion-like Me3SindashFndashAl(ORF)3 as well as the [NBu4]+[FAl(ORF)3]ndash and
[Ag(solvent)3]+[FAl(ORF)3]ndash or [Ag(solvent)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash salts (solvent =
toluene PhndashF)
E1 Syntheses
E11 Syntheses with Al(ORF)3 PhndashFrarrAl(ORF)3
E111 Synthesis of Me3SindashFndashAl(ORF)3 (E-1) The ion-like compound Me3SindashFndashAl(ORF)3
(E-1) was first prepared by reacting Ag+[Al(ORF)4]ndash with Me3SiCl giving AgCl
quantitatively C4F8O (measured) and Me3SindashFndashAl(ORF)3 (E-1) (yield 070 g 85 ) (Eq E-1
a))
a) Ag+[Al(ORF)4]ndash + Me3SiCl
Me3SindashFndashAl(ORF)3 (E-1)
CH2Cl2243 K to 298 K
253 Kn-hexane
(Eq E-1)
ndashC4F8O
ndash3EtH
ndashAgCl
b) AlEt3 + 3 HORF + FSiMe3
∆H(0 K) = ndash88 kJ molndash1
More conveniently and without anion decomposition is the second route in which in situ
prepared Al(ORF)3 and gaseous FSiMe3 which was condensed onto the formed Lewis
Superacid Al(ORF)3 (cf Eq E-1) react giving Me3SindashFndashAl(ORF)3 (E-1) (373 g 80 ) (Eq
E-1 b)) Al(Et)3 and FndashSiMe3 likely form the known Me3SindashAlEt3 complex[14] which
undergoes further solvolysis with RFndashOH Compared to the 19F signal of the AlndashF moiety in
the almost ldquonakedrdquo [FAl(ORF)3]ndash (E-5) (see below) the analogous 19F signal of E-1 is high
field shifted (from ndash1468 ppm (E-5) to ndash1561 ppm (E-1)) This has also been supported by
57
quantum mechanical calculations (BP86SV(P) level) ndash153 ppm for [FAl(ORF)3]ndash and ndash166
ppm for Me3SindashFndashAl(ORF)3
E112 Fluoride ion abstraction from [BF4]ndash-salts Salts of the [FAl(ORF)3]ndash-anion may be
prepared with pure donor-free Al(ORF)3 and Cat+[BF4]ndash in n-pentane under fluoride
abstraction and formation of BF3 (cf Eq E-7) The availability of the fluoride delivering
compound is important Reactions with LiBF4 did not lead to success probably because the
solubility of the lithium salt was to low in the tested solvents Earlier preparations[15] clearly
demonstrated that reactions of Al(ORF)3 with less soluble metal mono fluorides MF (M = Cs
Tl or Ag) were not suited to deliver well defined products
Cat+[BF4]ndash + AlMe3 + RFOH n-pentane
Cat+[FAl(ORF)3]ndash + 3CH4 + BF3
(Eq E-2)
273 K
cat+ = cation (cationic complex) Ag+ [N(Bu)4]+ no Li+
The preparation of Ag+[FAl(ORF)3]ndash succeeded in n-pentane at 273 K using a gas cooler set to
ndash30degC to avoid releasing the extremely volatile alcohol from the system (bp RFOH = 318 K)
The solid fluorinated metal salt is added bit by bit to the white precipitated Al(ORF)3 During
the quantitative formation of gaseous BF3 (measured) Ag+[FAl(ORF)3]ndash forms as light beige
product Changing to the larger [N(Bu)4]+ cation (Eq E-2) the reaction succeeds analogously
and forms the compound [N(Bu)4]+[FAl(ORF)3]ndash in almost quantitative yield Unfortunately
the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (crystallized from n-pentane) is only
preliminary (cf Crystal Structure Section J)
58
If excess Lewis acid Al(ORF)3 is present larger fluoride bridged anions form as described in
Eq E-3[16] The synthesis to the double fluoride bridged anion is herewith reduced to one step
instead of three steps as described in[15 17] synthesis of Li+[Al(ORF)4]ndash (1 step[17]) which
reacts with AgF to Ag+[Al(ORF)4]ndash (2 step[17]) and then with PCl3 giving Ag+[(RFO)3AlndashFndash
Al(ORF)3]ndash (3 step[15]) in a yield of 84 ) In the new one pot procedure (Eq E-3) the yield
of Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash increased to 86 (Ag+) or 89 ([N(Bu)4]+)
Cat+BF4ndash + 2AlMe3 + 6RFOH
n-pentane
Cat+[(RFO)3AlndashFndashAl(ORF)3]ndash + 6CH4 + BF3 (Eq E-3)
273 K
Cat+ = Ag+ [N(Bu)4]+ no Li+
Due to the risk of decomposition of pure Al(ORF)3 (vs) its fluorobenzene adduct complex
PhndashFrarrAl(ORF)3 may be applied as alternative since it features a higher stability
Furthermore the complex is a considerable better starting material for the synthesis of the
silver salt due to less side reactions The formation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3)
succeeded in an one pot reaction adding AgBF4 to PhndashFrarrAl(ORF)3
PhndashF Al(ORF)3 + AgBF4
in PhndashF
[Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) (Eq E-4)
E113 Solvates of Ag+[FAl(ORF)3]ndash and Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash If the obtained silver
salt Ag+[FAl(ORF)3]ndash (cf Eq E-2) is recrystallized from aromatic solvents (arenes cf Eq E-
5) such as toluene or FndashPh at 278 K the silver cation saturates by a threefold coordination to
59
the aromatic rings In both reactions colorless crystals have been formed and
[Ag(tol)3]+[FAl(ORF)3]ndash (E-2) as well as [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) could be isolated
Ag+[A]ndash + 3arenerecryst
[Ag(arene)3]+[A]ndash
[A]ndash = [FAl(ORF)3]ndash arene = toluene fluorobenzene[A]ndash = [(FRO)3AlndashFndashAl(ORF)3]ndash arene = 12-difluorobenzene (Eq E-5)
Similarly recrystallization of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash from 12ndashF2C6H4 at 273 K (cf Eq
6) leads to [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-4)
E114 Solution behavior of Ag+[FAl(ORF)3]ndash in CH2Cl2 According to Eq E-6 the possible
dismutation of 2[FAl(ORF)3]ndash (a) in poorly solvating CH2Cl2 to give [Al(ORF)4]ndash and
[F2Al(ORF)2]ndash (c) (∆solvGdeg = 19 kJ molndash1) has also been supported by ESI-MS spectroscopy
which always includes signals to [Al(ORF)4]ndash (cf Chapter J) This dismutation is also evident
from the side reaction described in Eq E-8 below However a hypothetic dimerization of two
[FAl(ORF)3]ndash species to form [(FAl(ORF)3)2]2ndash (b) is unfavored by 154 kJ molndash1
2[FAl(ORF)3]ndash (a)
FAl(ORF)3]2ndash (b)[(ROF)3Al
F
[F2Al(ORF)2]ndash + [Al(ORF)4]ndash (c)
(Eq E-6)∆solvGdeg in kJ molndash1
∆solvGdeg = 19
∆solvGdeg = 154 ∆solvGdeg = ndash134
oligomerizationinsoluble
60
E115 Formation of [Ph3C]+[FAl(ORF)3]ndash (E-4) Now the synthetic potential of
Ag+[FAl(ORF)3]ndash will be investigated The metathesis of Ag+[FAl(ORF)3]ndash with Ph3CCl in
CH2Cl2 at room temperature gives [Ph3C]+[FAl(ORF)3]ndash (E-4) (Eq E-7) Crystals of E-4 have
been obtained by cooling the filtrate to 243 K (non optimized crystalline yield 016 g 14
however according to solution NMR the reaction is quantitative)
Ag+[FAl(ORF)3]ndash + CPh3ClCH2Cl2
[Ph3C]+[FAl(ORF)3]ndash (E-4) + AgCl (Eq E-7)
rt
In Fig E-6 below the crystal structure of E-4 is presented which proves as a compound with
an non coordinated [FAl(ORF)3]ndash-anion
E116 Side reactions Refluxing [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash Upon refluxing
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash in n-hexane the compound dismutates giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) Its hypothetic formation is detailed in
Eq E-8
2[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash 2[N(Bu)4]+ + 2Al(ORF)3 + 2[FAl(ORF)3]ndash (a)dissociation
dismutation
∆ n-hexane3 h
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)+ [N(Bu)4]+
+ [Al(ORF)4]ndash
2[N(Bu)4]+ + [F2Al(ORF)2]ndash + [Al(ORF)4]ndash + 2Al(ORF)3(b)
(c)
∆solvG343 K = 99∆solvGdeg = 60
∆solvG343 K = ndash206∆solvGdeg = ndash107
∆solvG343 K = 56∆solvGdeg = 42
∆solvG343 K = ndash48∆solvGdeg = ndash3
∆solvG in kJ molndash1 (Eq E-8)
Due to the size of the compounds the frequency calculations and thermal corrections to
enthalpy and free energy were only performed at the PM6 level[18] Total energies and
61
solvation energies stem from BP86SV(P) calculations According to the calculations included
with Eq E-8 the dissociation of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash into [N(Bu)4]+ Al(ORF)3
and 2[FAl(ORF)3]ndash in n-hexane may be possible by overcoming the free energy ∆solvG(343 K)
(99 kJ molndash1) (a) Also herein the formation of Al(ORF)4ndash as proposed in (c) and in Eq 6 (c)
was observed by ESI-MS spectroscopy However the trimerization of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash to give the doubly fluoride bridged anion
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) (b) proceeds by a gain of the energy of
ndash48 kJ molndash1 in boiling n-hexane Compound E-6 is stabilized by 206 kJ molndash1 amongst the
species in (c)
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash (E-6) may be described as a doubly bridged
Al(ORF)3-adduct complex of a central [F2Al(ORF)2]ndash-anion and features analogies to the very
strong Lewis acid SbF5 The known fluoro-anions of SbF5 are [SbF6]ndash [Sb2F11]ndash [Sb3F16]ndash and
[Sb4F21]ndash The analogous series of already known Fndash-adducts of Al(ORF)3 are [FAl(ORF)3]ndash
[(RFO)3AlndashFndashAl(ORF)3]ndash and now [(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash This comparison
demonstrates and underlines the inherent strength of the Lewis Superacid Al(ORF)3
E117 Representative NMR-Data of the Fluoroaluminates Table E-1 (see below) gives an
overview to relevant NMR-Data of compounds E-1 E-2 E-3 E-4 E-5 and E-6 as well as
[N(Bu)4]+[FAl(ORF)3]ndash and PhndashFrarrAl(ORF)3 that may be used for fast screening
62
Table E-1 19F and 27Al NMR data shifts of compounds E-1 to E-6 compared to PhndashFrarrAl(ORF)3[19]
[FAl(ORF)3]ndash
Compound δ 19F [ppm] AlndashF δ 19F [ppm] CF3 δ 27Al [ppm] Al PhndashFrarrAl(ORF)3
[19] ndash1440 s ndash755 s 365 s very broad ∆12 = 2350 Hz
[FAl(ORF)3]ndash (calc)a) ndash1529d) ndash659d) 362e)
Me3SindashFndashAl(ORF)3 (E-1) ndash1561 s ndash771 s 396 s very broad ∆12 = 960 Hz
Me3SindashFndashAl(ORF)3 (calc)a) ndash1661d) ndash669d) 465 [Ph3C]+[FAl(ORF)3]ndash (E-4) ndash1477 s ndash758 s 384 sc) ∆12 = 83 Hz [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) ndash1471 s ndash759 s 402 sc) ∆12 = 116 Hz [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) ndash1468 s ndash758 s 368 d 1JAlF = 470 Hz [N(Bu)4]+[FAl(ORF)3]ndashb) - - 420 sc) ∆12 = 2407 Hz [Ag(12ndashF2C6H4)3]+ [(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)g)
ndash1850 s ndash761 s 344 s broad
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6)
ndash1848 s ndash757 s 321 s broad ∆12 = 1740 Hz
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (calc)a)
ndash1890f) ndash765f) 345f)
a)calculated values at the BP86SV(P) level b)no 19F spectra have been measured c)instead of the expected doublet for [FAl(ORF)3]ndash a broad signal has been detected due to a dynamic sytem d)referred to CFCl3 as reference σ (19F) = 1956 ppm[20] e)referred to [Al(ORF)4]ndash (RF = C(CF3)3 as reference with δ (27Al) = 5692 ppm f)referred to [(RFO)3AlndashFndashAl(ORF)3]ndash as reference g)the compound E-5 was earlier synthesized its spectroscopic parameters are taken into account for comparison[21]
E2 Crystal Structures
Details of the crystallographic studies for compounds E-1 E-2 E-3 E-4 E-5 and E-6 are
listed at the end in Table E-2 Table E-3 Table E-4 Table E-5 The structure of Phndash
FrarrAl(ORF)3 will not be discussed independently[19] Details of the preliminary structure of
[N(Bu)4]+[FAl(ORF)3]ndash are given in Chapter J
Structures including the [FndashAl(ORF)3]ndash anion
The structural data of compounds PhndashFrarrAl(ORF)3 E-1 E-2 and E-4 are compared in Table
E-2 in which also the bonding situation around the central atoms Al F Ag and Si is analyzed
by I D Browns bond valence method[22]
63
E21 Me3SindashFndashAl(ORF)3 (E-1) The average lengths of the three AlndashO single bonds of 1708
Aring are about 1 pm longer than in the molecule PhndashFrarrAl(ORF)3 (1694 Aring) and indicates the
slightly stronger donor capacity of Me3SindashF vs PhndashF[19]
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig E-1 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (E-1) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths in [Aring] and angles in [deg] are included in Table E-2 The H-atoms are given as balls
The relatively large Si(1)ndashF(1)ndashAl(1) angle of 14644(8)deg is indicative for an rather ionic Alndash
F interaction Compared to Willnerrsquos compound [Me3Si]+[RCB11F11]ndash (with R = H C2H5)[30]
the corresponding SindashF bond length in E-1 is by 013 Aring shorter (1744 Aring cf
[Me3Si]+[RCB11F11]ndash 1878 Aring) This elongation and weaker coordination may be referred to
the less coordinating carboranate anion The AlndashF distance in E-1 is elongated by about 0025
Aring in comparison to E-5[21] (range 1768 to 1782 Aring av 1775 Aring) In the fluoride bridged
anion of E-5 the two Lewis acidic Al centers share the F-atom thus a stronger and therefore
shorter AlndashF contact in E-5 results Further comments on the structure will be given in a later
section
E22 [Ag(arene)3]+[FAl(ORF)3]ndash (E-2 arene= toluene E-3 arene = fluorobenzene) The
core of these structures consist of an FAlO3 unit The three AlndashO bond lengths (1733(2)(av) Aring)
64
and the AlndashF distance (16814(19) Aring) of E-2 are in good agreement to those found in the
preliminary structure of E-3 (17291(1)(av) Aring 1656(6) Aring) (cf also Fig E-2 Fig E-3 and
Table E-2)
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
O3
O1O2
F1Ag1
C5
C1
C9
C23
C22
C30
C16
C15Al1
Fig E-2 Section of the crystal structure of [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) at 150 K with thermal displacement
ellipsoids showing 50 probability The H-atoms are given as balls The most important atom labels are given
in the figure Selected bond lengths are included in Table E-2
The weak coordination of Ag+ to [FAl(ORF)3]ndash in E-2 and E-3 is balanced by the coordination
of three arene rings (E-2 toluene E-3 fluorobenzene) to the silver atom In E-2 two of them
are η2 and one is η1 carbon coordinated by contrast in E-3 all rings are η2 coordinated Due to
the preliminary nature of structure E-3 the herein further discussed parameters are reduced to
the most important central atoms Ag1 F1 and Al2 The aromatic rings in E-2 and E-3 are
nearly all in a right angle position to the F(1) atom In E-2 the angles are C(15)ndashAg(1)ndashF(1)
8084(9)deg C(30)ndashAg(1)ndashF(1) 9108(10)deg and C(23)ndashAg(1)ndashF(1) 8614(10)deg which the most
appropriate position between intra- and inter-molecular repulsion of the rings
65
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
F1
Al2
O2
O3
O1
C41C46
C63
C64C54C53
Fig E-3 Section of the preliminary crystal structure of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (E-3) at 150 K Due to
disorder in the anion and inherent bad crystal quality the atoms are described as balls The cationic parameters
are described in Table E-5 The most important atom labels are given in the figure Selected bond lengths in [Aring]
and angle in [deg] Ag(1)ndashF(1) 2468 (bond valance 0094 cf Table E-5)[22] F(1)ndashAl(2) 1652 (bond valance
0749 cf Table 5)[22] Ag(1)ndashF(1)ndashAl(2) 151747
Compared to the former structure E-2 the AgndashF contact in E-3 is shortened by 008 Aring (2544
Aring (E-2) 2468 Aring (E-3)) which is consistent with toluene being a stronger donor than
fluorobenzene As consequence Ag+ in [Ag(FndashPh)3]+ becomes more electrophilic and the
distance between AgndashF decreases compared to E-2 The long AgndashF bond in E-2 and the
slightly smaller one in E-3 demonstrate the very weak coordinating force of the [FAl(ORF)3]ndash-
anion A comparable shorter AgndashF contact with 2487 Aring has already been reported in the
literature[23] Therein the smaller distance may be referred to the sterical less demanding BF3
rest of the coordinated BF4ndash-anion compared to the bigger Al(ORF)3 grouping of the
[FAl(ORF)3]ndash-anion in E-2 and E-3
However apart from those aspects [FAl(ORF)3]ndash features being a very good candidate for
weak coordination and chemical robustness of highly electrophilic cationic complexes and
their stabilization (cf E-1) If referred to Ag+-species Reed et al as well as Xie et al reported
66
on other [Ag(arene)x]+ (arene = xylol x = 1 2) complexes coordinated to carboranate anions
[CB11H6Cl6]ndash[24] and [1-HndashCB11Cl5Br5]ndash[25] known to be a very robust and stable anion In the
corresponding anion[24] the AgndashCl distances are with 2679 Aring (bond valance AgndashCl 0185[22])
and 2926 Aring (bond valence AgndashCl 0095[22]) indeed much longer than the AgndashF bonds in E-2
but the larger bond valence of 0185 demonstrates the stronger coordination ability of Ag+ to
Cl than Ag+ to F in E-3 The analogue bond lengths in Xiersquos carboranate anion[25] are 2708 Aring
(bond valence AgndashCl 0171[22]) and 2871 Aring (bond valence AgndashCl 0110[22]) Certainly the
bond elongations of AgndashCl compared to AgndashF may be referred to the sterical demand of the
carboranate anions their larger Cl-atoms and to the electron donating xylol groups in Reedrsquos
and Xiersquos compounds Evidently the valence bond analyses of ID Brown[22] demonstrates
clearly the weaker coordination ability of [FAl(ORF)3]ndash to Ag+ than those carboranates to the
silver cation
E23 [Ph3C]+[FAl(ORF)3]ndash (E-4) The core of this molecule (Fig E-4) also consists of an
FAlO3 unit as in E-2 and E-3 but in this case completely uncoordinated The average lengths
of the three AlndashO single bonds at 1730(3) Aring is similar to the ones in the homoleptic
[Al(ORF)4]ndash anion (1725 Aring)[26] Compared to the other AlndashF distances reported in here the
Al(1)ndashF(1) bond is further shortened to 1660(3) Aring which is comparable with the analogue
distance in E-3 (1656(6) Aring)
67
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig E-4 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (E-4) at 100 K with thermal displacement
ellipsoids showing 50 probability The most important atom labels are given in the figure Selected bond
lengths are given in Table E-2
For comparison in slightly silver coordinated E-2 d(AlndashF) is 1681(2) Aring in ion-like E-1 it
rises to 1803(1) Aring and in the weak complex PhndashFrarrAl(ORF)3 it reaches its maximum in this
series at 1864(2) Aring Thus the AlndashF distance in E-4 (1660(3) Aring) is the shortest in this series
and is in agreement with an undisturbed almost ldquonakedrdquo [FAl(ORF)3]ndash anion
E231 Comparison of the [FAl(ORF)3]ndash Structures The details of structures of E-1 E-2
E-4 and PhndashFrarrAl(ORF)3 are compared in Table E-2 For a more quantitative investigation of
the bonding situation around the central atoms of structures E-1 E-2 E-4 and Phndash
FrarrAl(ORF)3 I D Brownrsquos[22] bond valence analysis was performed (cf Table E-2)
AlndashO bonds In the compounds E-1 E-2 and E-4 the AlndashO bond valences are appreciable
smaller than in PhndashFrarrAl(ORF)3 due to the lower electron density around the central Al-atom
in the weakly bounded fluorobenzene adduct complex
68
AlndashF bonds Due to the longer AlndashF bond distances in PhndashFrarrAl(ORF)3 and E-1 the bond
valences are smaller than in E-2 and E-4 The highest value of 0733 of E-4 is in agreement
with [FAl(ORF)3]ndash being an unhindered anion
Table E-2 Most important bond lengths and angles as well as the bond valences of Al(ORF)3-compounds E-1
E-2 and E-4 compared to literature values of PhndashFrarrAl(ORF)3[19]
Param PhndashFrarrAl(ORF)3
bond length [Aring] angle [deg][19]
bond valence
Σ(bond valences)
Me3SindashFndashAl(ORF)3 (E-1) bond length [Aring] angle [deg]
bond valance
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1706(2) 0971 Al 3426 Al(1)ndashO(1) 17112(14) 0966 Al 3421 Al(1)ndashO(2) 1693(2) 1005 Al(1)ndashO(2) 17064(16) 0978 Al(1)ndashO(3) 1685(2) 1027 Al(1)ndashO(3) 17062(15) 0979
AlndashF Al(1)ndashF(1) 18636(18) 0423 Al(1)ndashF(1) 18031(13) 0498 SindashF - - - Si(1)ndashF(1) 17439(13) 0702 Si 4101SindashC - - - Si(1)ndashC(2) 1836(2) 1135
- - - Si(1)ndashC(3) 1838(2) 1129 - - - Si(1)ndashC(1) 1836(2) 1135
lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1158(1) - - O(3)ndashAl(1)ndashO(2) 11408(8) - - O(3)ndashAl(1)ndashO(1) 1214(1) - - O(3)ndashAl(1)ndashO(1) 12099(8) - - O(2)ndashAl(1)ndashO(1) 1132(1) - - O(2)ndashAl(1)ndashO(1) 11031(7) - -
lt(OndashAlndashF) O(1)ndashAl(1)ndashF(1) 9530(9) - - O(1)ndashAl(1)ndashF(1) 9894(7) - - O(2)ndashAl(1)ndashF(1) 1030(1) - - O(3)ndashAl(1)ndashF(1) 10383(7) - - O(3)ndashAl(1)ndashF(1) 10283(9) - - O(2)ndashAl(1)ndashF(1) 10615(7) - -
Param [Ag(tol)3]+[FAl(ORF)3]ndash (E-2) bond length [Aring]
angle [deg]
bond valence
Σ(bond valences)
[Ph3C]+[FAl(ORF)3]ndash (E-4) bond length [Aring] angle [deg]
bond valence
Σ(bond valences)
AlndashO Al(1)ndashO(1) 1732(2) 0913 Al 3423 Al(1)ndashO(1) 1738(3) 0890 Al 3473 Al(1)ndashO(2) 1735(2) 0905 Al(1)ndashO(2) 1728(3) 0915 Al(1)ndashO(3) 1732(2) 0913 Al(1)ndashO(3) 1720(3) 0935
AlndashF Al(1)ndashF(1) 16814(19) 0692 Al(1)ndashF(1) 1660(3) 0733 - lt(OndashAlndashO) O(3)ndashAl(1)ndashO(2) 1140(1) - - O(3)ndashAl(1)ndashO(2) 1108(2) - -
O(3)ndashAl(1)ndashO(1) 1078(1) - - O(3)ndashAl(1)ndashO(1) 1079(2) - - O(2)ndashAl(1)ndashO(1) 1082(1) - - O(2)ndashAl(1)ndashO(1) 1079(2) - -
lt(OndashAlndashF) O(3)ndashAl(1)ndashF(1) 1058(1) - - O(3)ndashAl(1)ndashF(1) 1082(2) - - O(1)ndashAl(1)ndashF(1) 1118(1) - - O(1)ndashAl(1)ndashF(1) 1100(2) - - O(2)ndashAl(1)ndashF(1) 1102(1) - - O(2)ndashAl(1)ndashF(1) 1121(2) - -
E232 Establishing the ion-like character of Me3SindashFndashAl(ORF)3 (E-1)
Considering the fact that the SindashF bond is very elongated E-1 can be seen not only as an
adduct of Me3SiF to Al(ORF)3 but also as a silylated WCA The strongest commonly used
silylaing agent is trimetylsilyl triflate and to give a benchmark for the silyl donor capability
of E-1 we calculated the thermodynamic functions of the silyl group exchange between the
69
[FndashAl(ORF)3]- and the triflate anion using the BP86 functional in combination with the SV(P)
basis set for all atoms In the gas phase the reaction enthalpy between E-1 and [SO3CF3]ndash is
strongly exothermic with ∆rHdeg of ndash160 kJ molndash1 at 298 K Since the sum of particles is
constant in the reaction and thus the entropy change is low the calculated free reaction
enthalpy differs just slightly giving ∆rGdeg of ndash170 kJ molndash1 at 298 K In solution these values
should be less negative because of the stronger solvation of the smaller triflate anion
compared to the [FndashAl(ORF)3]ndash The free solvation enthalpies in dichloromethane (εr = 893)
using the COSMO[27] model have been calculated a Born-Haber cycle to evaluate the
reaction thermodynamics in CH2Cl2 solution quantumchemically has been constructed An
overview of the calculated free enthalpies is shown in the below sketched Scheme E-1
Me3SindashFndashAl(ORF)3(solv) + [SO3CF3]ndash(solv) [FndashAl(ORF)3]ndash
(solv) + Me3SindashSO2CF3(solv)CH2Cl2
∆Gdeg = ndash88 kJmol
Me3SindashFndashAl(ORF)3(g) + [SO3CF3]ndash(g) [FndashAl(ORF)3]ndash
(g) + Me3SindashSO2CF3(g)
ndash∆solvGdeg
+9 kJmolndash∆solvGdeg
+195 kJmol
∆solvGdeg
ndash113 kJmol∆solvGdeg
ndash9 kJmol
gas phase∆rGdeg = ndash170 kJmol
(Scheme E-1)
Since the triflate anion is by 82 kJ molndash1 stronger solvated than the aluminate the reaction is
less exergonic in dichloromethane than in the gas phase but E-1 is a much stronger silyl
donor than trimethylsilyl triflate
Overall E-1 can be considered to be an ion-like compound an electronic and structural
hybrid of covalent Me3SindashFndashAl(ORF)3 and ionic [Me3Si]+[FAl(ORF)3]ndash species[6] To the
knowledge this moiety is the first example of the [FAl(ORF)3]ndash anion in an ion-like species
(cf Scheme E-2) In contrast to the related complex AlEt3FSiMe3[14] which is a liquid the
70
novel material can be crystallized Since two decades silylium ions have been of current
interest in many spectroscopic and structural characterizations[6 8 28] As one reference for
cationic character the sum of the CndashSindashC bond angles is considered to be adequate for this
classification The below sketched Scheme E-2 illustrates the difference between covalent
ion-like and ionic species In E-2 the sum of the CndashSindashC bond angles is 346deg and may
therefore classified as an ion-like compound
Si Y109deg Si Y117deg Si Y120deg
Σ (CndashSindashC) = 337deg Σ (CndashSindashC) = 345deg - 354deg Σ (CndashSindashC) = 360deg
covalent ion-like ionic
δ+ δminus minus+
Scheme E-2 Illustration of the three different bond types in an R3Si+Yndash compound (R = eg Me Et i-Pr Y =
eg [CB11H6X6]ndash (X = Cl Br)[6] [FAl(ORF)3]ndash)
The sum of the CndashSindashC angles (346deg) in E-1 is much smaller than in eg Willnerrsquos almost
ionic [Me3Si][RCB11F11] (with R = H C2H5)[29] with 354deg due to the larger and less
coordinating carboranate anion Table E-3 compares the bonding situations between the
compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[26] and Me3SiF[30] analyzed with I
D Brownrsquos program[22]
E233 Bonding around Si in the ion-like E-1 The bond valence analysis clearly
demonstrates that the F-atom in E-1 is a bit stronger bound to the Si-atom (0702) than to the
Al-atom of the [FAl(ORF)3]ndash-anion (0498) and to Willnerrsquos [Me3Si]+[C2H5CB11F11]ndash[29]
(0459) (cf Table E-3) which confirms the ion-like[6] character of E-1 The silylium group
[Et3Si]+ of Reedrsquos Et3Si(CHB11Cl11)[31] is in analogy to Willnerrsquos compound weakly
71
coordinated to carborantes (via F[29]) If referred to F the silylium group is even weaker
coordinated than to Cl (0491) (cf Table E-3)
Table E-3 Comparison between the compounds [Me3Si][C2H5CB11F11][29] Et3Si(CHB11Cl11)[31] Me3SiF[30] Me3SindashFndash
AlEt3[14]
their bond situation and 1H NMR data
Compound (SindashC)av [Aring] (bond valanceav)
SindashX [Aring] (X = Cl F) (bond valence)
Σ(Si bond valencesav)
Σ(CndashSindashC) [deg]
δ1H(Me3Si) [ppm] (3JSiH [Hz])
[Me3Si]+[C2H5CB11F11]ndash[29] 1823 (1176) 1901 (0459) (X = F) 3987 354 not comparable1) Et3Si(CHB11Cl11)[31] 1845 (1108) 2334 (0491) (X = Cl) 3815 350 not comparable Me3SindashFndashAl(ORF)3 1836 (1135) 1744 (0702) (X = F) 4210 346 044 d2) (1321)3) Me3SindashFndashAlEt3
[14]4) - - - - ndash018 d (705)5) Me3SiF[30] 1848 (1131) 1600 (1036) (X = F) 4333 335 033 d2) (740)6)
1)[Me3Si]+[C2H5CB11F11]ndash was measured in CD3CN at 298 K which may form [Me3SindashNCndashMe]+ in solution 2)taken in CD2Cl2 at 298 K 3)no 1JSiF coupling could be detected due to a singlet in the 19F NMR spectrum at ndash1561 ppm 4)no crystal structure was given 5)no 1JSiF coupling was given 6)1JSiF = 274 Hz
Summarizing all the ideas the weakly coordinating anion [FAl(ORF)3]ndash proves as a very
stable and chemically robust anion which may even undecomposed coordinate highly
electrophilic compounds such as [Me3Si]+ The silylium group is stronger coordinated to the
[FAl(ORF)3]ndash in E-1 than in Willnerrsquos or Reedrsquos compounds however the compound is still
very stable and as the Me3Si-exchange with CF3SO3SiMe3 above has shown should prove as
a valuable ion-like ldquo[Me3Si]+rdquo agent
E24 Structures with AlndashFndashAl bridges The structures with fluoride bridged anions
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] and [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndash
FndashAl(ORF)3]ndash (E-6) are shown in the below sketched Fig E-5 and Fig E-6 The core
structural parameters of both anions are discussed in context below near Table E-4 those of
the [Ag(12ndashF2C6H4)3]+-cation of E-5 are compared together with the other [Ag(arene)3]+
structures in a later section
72
E241 [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] The anion may be considered
to be an Al(ORF)3 adduct complex of the [FAl(ORF)3]ndash-anion (Fig E-5) which also has been
earlier synthesized and published[15]
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig E-5 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] at 100 K with
thermal displacement ellipsoids showing 50 probability The most important atom labels are given in the
figure The structure of the anion [(RFO)3AlndashFndashAl(ORF)3]ndash was solved with disorder in three different
independent CF3 groups with the ratio of 6832 6337 8812 [] Selected bond lengths are given in Table E-4
(anion) and Table E-5 (cation)
E242 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) The anion [(RFO)3AlndashFndash
Al(ORF)2ndashFndashAl(ORF)3]ndash (Fig E-6) may be described as a doubly bridged Al(ORF)3-adduct
complex of a central [F2Al(ORF)2]ndash-anion
73
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
F100 F101
Al2
O4
C13
C17
C9 C5
C1
O1
C29
O8
C21
O6 O8
Al3 Al1
C25
Fig E-6 Section of the crystal structure of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) at 150 K with
thermal displacement ellipsoids showing 50 probability For a better overview the [N(Bu)4]+ cation is omitted
The most important atom labels of the center of the anion are given in the figure Selected bond lengths are given
in Table E-4 (anion)
Table E-4 Most important bond lengths in the anions and angles as well as the bond valences of E-5[21] and E-6
Parameter E-5[21] bond length [Aring] angle [deg]
bond valence
Σ bond valences
E-6 bond length [Aring] angle [deg]
bond valence
Σ bond valences
AlndashO Al(3)ndashO(7) 1710(4) 0969 Al(3) Al(1)ndashO(2) 1695(5) 1009 Al(1) Al(3)ndashO(9) 1712(4) 0963 3442 Al(1)ndashO(3) 1698(5) 1001 3475 Al(3)ndashO(8) 1712(4) 0963 Al(1)ndashO(1) 1705(4) 0982 Al(4)ndashO(10) 1706(4) 0979 Al(4) Al(2)ndashO(4) 1693(4) 1014 Al(2) Al(4)ndashO(11) 1708(4) 0974 3438 Al(2)ndashO(5) 1698(4) 1001 3186 Al(4)ndashO(12) 1714(4) 0958 Al(3)ndashO(6) 1699(5) 0998 Al(3) - - Al(3)ndashO(8) 1700(4) 0995 3486 - - Al(3)ndashO(7) 1702(4) 0990
AlndashF Al(3)ndashF(203) 1768(4) 0547 Al(1)ndashF(101) 1814(4) 0483 Al(4)ndashF(203) 1782(4) 0527 Al(2)ndashF(100) 1739(4) 0592 - - - Al(2)ndashF(101) 1747(4) 0579 - - - Al(3)ndashF(100) 1799(4) 0503
lt(AlndashOndashC) Al(3)ndashO(7)ndashC(25) 1500(4) - - Al(1)ndashO(1)ndashC(1) 1456(5) - - Al(3)ndashO(8)ndashC(29) 1468(4) - - Al(1)ndashO(2)ndashC(5) 1471(4) - - Al(3)ndashO(9)ndashC(33) 1496(4) - - Al(1)ndashO(3)ndashC(9) 1496(5) - - Al(4)ndashO(10)ndashC(37) 1524(4) - - Al(2)ndashO(4)ndashC(13) 1446(5) - - Al(4)ndashO(11)ndashC(41) 1492(4) - - Al(2)ndashO(5)ndashC(17) 1452(4) - - Al(4)ndashO(12)ndashC(45) 1450(4) - - Al(3)ndashO(6)ndashC(21) 1489(4) - - - - - Al(3)ndashO(7)ndashC(25) 1480(4) - - - - - Al(3)ndashO(8)ndashC(29) 1504(4) - -
lt(AlndashFndashAl) Al(3)ndashF(203)ndashAl(4) 1783(2) - - Al(2)ndashF(100)ndashAl(3) 1672(2) - - - - - Al(2)ndashF(101)ndashAl(1) 1703(2) - -
74
E2421 Comparison of the structural parameters of the fluoride bridged anions The
structural parameters of the anion in E-5 are in good agreement with those found in
[Ag(CH2Cl2)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash[15] The AlndashF and AlndashO bonds (OndashAlndashO) and (Alndash
OndashC) bond angles are with 1775(av) Aring (d(AlndashF)range 1768(4) - 1782(4) Aring) 1710(av) Aring (d(Alndash
O)range 1708(4) - 1714(4) Aring) 11347deg(av) (lt(OndashAlndashO)range 1102 - 1181deg) and 14883deg
(lt(AlndashOndashC)range 1450 - 1524deg) similar to those in[15] Compared to the corresponding bond
lengths in E-6 the average AlndashO distances (1699 Aring) are herein relatively short and closer to
the situation of those in the Lewis acid PhndashFrarrAl(ORF)3 (1695 Aring) or the ion-like compound
E-1 (1708 Aring) The two AlndashF bonds to the Al(ORF)3 moieties (d(AlndashF)(av) = 1807 Aring) are by
0064 Aring(av) longer than those around the central [F2Al(ORF)2]ndash-anion (d(AlndashF)(av) 1743 Aring)
The bond situation around the Al-atom in the Al(ORF)3 units of both anions is in good
agreement and similar to those found in PhndashFrarrAl(ORF)3[19] E-1 E-2 and E-4 (cf Table E-
2) Hence the coordinated F-atom to the acidic Al central atom remains with a very small
bond valence By contrast the F2Al(ORF)2 unit indicates that the two F-atoms are stronger
coordinated to the Al(2)-atom than to the others (Al(1) and Al(3)) and share their bond
valence by 1171 (ΣAl 3186) The bulky ORF-groups have very wide AlndashOndashC bond angles
of 1474deg(av) indicative for a very polar and almost ionic bonding For the same reason the two
AlndashFndashAl angles (1688deg(av)) are almost linear It appears that the steric requirements of the
bulky Al(ORF)3 moieties induce the small deviation from linearity
E2422 [FAl(ORF)3]- as an WCA Comparison of the structures of [Ag(arene)3]+-salts of
[(RFO)3AlndashFndashAl(ORF)3]ndash and [FAl(ORF)3]ndash (Table E-5) The local coordination of the silver
cation stabilized by arene rings as in [Ag(arene)3]+ (E-2 and E-3) demonstrates the weakly
coordinating nature of the [FAl(ORF)3]ndash-anion via the F-atom Compared to the ldquonakedrdquo
[Ag(arene)3]+ in E-5 the sum of the bond valances in E-2 (0988) is almost unchanged (E-5
0982) and the AgndashF valence is very low at 0076
75
Table E-5 Comparison of the bond paramenters in the [Ag(arene)3]+-cations of E-2 (arene= toluene)
E-3 (arene = fluorobenzene) and E-5 (arene = difluorobenzene)
Param [Ag(tol)3]+[FAl(ORF)3]ndash
(E-2) bond length [Aring] bond valence
[Ag(PhF)3]+[FAl(ORF)3]ndash
(E-3) bond length [Aring] bond valence
[Ag(F2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5)[21] bond length [Aring]
bond valence
AgndashF Ag(1)ndashF(100) 2544(2) 0076 Ag(1)ndashF(1) 2468(2) 0094 - - AgndashC Ag(1)ndashC(16) 2502(4) 0189 Ag(1)ndashC(53) 2683(3) 0116 Ag(2)ndashC(202) 2470(7) 0206 Ag(1)ndashC(15) 2508(4) 0186 Ag(1)ndashC(54) 2718(4) 0106 Ag(2)ndashC(215) 2494(6) 0193 Ag(1)ndashC(22) 2513(4) 0184 Ag(1)ndashC(46) 2804(5) 0084 Ag(2)ndashC(208) 2547(6) 0168 Ag(1)ndashC(23) 2529(4) 0176 Ag(1)ndashC(41) 2582(4) 0153 Ag(2)ndashC(203) 2584(7) 0152 Ag(1)ndashC(30) 2527(4) 0177 Ag(1)ndashC(64) 2533(3) 0174 Ag(2)ndashC(214) 2594(8) 0148 - - Ag(1)ndashC(63) 2599(4) 0146 Ag(2)ndashC(207) 2688(7) 0115 Σ(bond valences) Ag 0988 Σ(bond valences) Ag 0873 Σ(bond valences) Ag 0982
Analogously to E-2 and E-3 the silver atom in E-5[21] is coordinated by three arene rings All
of the latter in E-3 and E-4 are η2 coordinated This is in contrast to E-2 where two toluene
rings are η2 and one is η1 coordinated The AgndashC bond lengths are a function of the donor
capacity of the arene Hence the AgndashC bonds are shortest for the most electron rich arene
toluene (range 2502 - 2529 Aring) and elongated in E-5 for the most electrondeficient arene
difluorobenzene by 004 Aring (2563 Aring(av) range 2470 - 2689 Aring) In E-3 the corresponding
AgndashC bond lengths are elongated up to 2804 Aring (range 2533 - 2804 Aring 2563 Aring(av)) but the
AgndashF bond is shortened to 2468 Aring while the sum of the bond valences around the silver
atom remains nearly constant This AgndashC lengthening occurs despite the fact that the Ag+
cation in E-2 and E-3 is further saturated by a weak AgndashF contact The small valence bonds
for this contact (E-2 0076 E-3 0094) prove the weakly coordinating property of the F
coordination to the cationic silver complex According to a search in the CSD database
compound E-4 includes the first example for a naked homoleptic [Ag(arene)3]+ complex
Even the more bulky weakly coordinating carboranate anions are not able to stabilize such
[Ag(arene)3]+ complexes (for [Ag(arene)]x-structures (x = 1) stabilized with carboranates cf
ie PhAg[B11CH12][32] or MesAg(NCCH3)[B11CBr12][25] for x = 2 ie
Mes2Ag[B11CBr7Cl5][25]) This is in agreement with [FAl(ORF)3]ndash being a weaker
76
coordinating anion than the carboranate The coordinating ability of both anions is supported
by the resultant equilibration between Ag(arene)x[WCA] Ag(arene)x-1[WCA] + arene
(x = 1-3) For WCA = [FAl(ORF)3]ndash the position is on the left side and for WCA =
carboranate on the right side
E3 IR-Spectroscopy of the [FAl(ORF)3]ndash-salts E-1 to E-4 In Table E-6 (see below) the spectroscopical IR data of all salts containing the [FAl(ORF)3]ndash-
anion in this chapter are demonstrated
77
Table E-6 IR spectroscopic analyses of compound PhndashFrarrAl(ORF)3 = A[19] E-1 to E-4 compared to calculated
IR bands of [FAl(ORF)3]ndash and Me3SindashFndashAl(ORF)3 (E-1)
A [cmndash1] exp
A [cmndash1] calc1)
E-1 [cmndash1] exp
E-1 [cmndash1]calc1)
E-2 [cmndash1] exp
E-3 [cmndash1] exp
E-4 [cmndash1] exp
[FAl(ORF)3]ndash
[cmndash1] calca) - - - 444 (w) 453 (w) - 448 (w) 439 (w)
455 (w) 466 (w) 453 (w) 455 (w) 458 (sh) 465 (w) 468 (w) - - - - - 518 (mw) - - 520 (mw)
537 (w) 528 (w) 537 (w) - 538 (w) 539 (w) 537 (w) 547 (mw) 574 (w) 578 (w) 576 (w) 567 (w) - - - - 583 (w) 594 (w) - 595 (w) 609 (w) 609 (w) 609 (w) -
- - - 633 (m)b) - - 623 (w)b) - - - - - - - 641 (vw) -
668 (w) 676 (w) 661 (w) - 668 (w) 663 (w) 660 (sh) 709 (m) - - 703 (w) 708 (w) - 690 (w) 701 (s) - - - - 711 (w) - 710 (w) - -
726 (vs) 727 (vs) 728 (vs) - 729 (vs) 725 (s) 727 (vs) 735 (w) - - - - - 756 (w) - -
746 (s) 743 (s) 770 (w) 762 (w) - 769 (w) 766 (s) - - - - - 795 (vw) 778 (w) 807 (w) 808 (w) - - - - - 809 (w) 826 (ms) -
846 (ms) 865 (ms) 857 (ms) 855 (m) 846 (vw) 838 (w) 840 (ms) 841 (w) 889 (w) 894 (w) - 876 (m) - - - - 913 (w) 903 (w) - 878 (m) - 907 (w) 916 (vw) - 971 (vs) 969 (vs) 976 (vs) 966 (s) 976 (vs) 967 (vs) 972 (vs) 961 (s)
1017 (ms) 1015 (ms) - - - 999 (w) 997 (ms) - - - - - - 1015 (w) 1029 (ms) -
1074 (ms) 1062 (ms) - - - 1065 (w) 1060 (ms) - - - 1100 (w) - - - 1099 (ms) 1111 (w)
1153 (s) 1158 (s) 1165 (s) 1158 (w) - 1158 (w) 1167 (s) 1132 (w) 1183 (s) 1180 (s) 1180 (s) 1220 (w) 1183 (s) 1172 (m) 1186 (s) - 1212 (s) 1213 (s) 1220 (s) 1202 (m) 1217 (s) 1212 (vs) 1214 (s) 1213 (vs)
- - - 1234 (s) - 1239 (vs) - - - - 1252 (vs) 1244 (vs) 1259 (vs) 1261 (s) 1263 (s) 1231 (vs) - - - 1265 (vs) - - 1280 (s) -
1301 (s) 1308 (s) - 1333 (w) 1299 (s) 1297 (m) 1298 (s) 1295 (vs) - - - - 1357 (s) 1350 (w) - 1333 (ms)
1358 (s) 1354 (s) 1356 (s) 1341 (w) 1370 (s sh) - 1363 (s) 1360 (w) - - - - - - 1375 (s) -
1456 (vw) - - - 1457 (s) 1454 (w) 1453 (vs) - - - 1468 (s) - - - 1466 (s sh) -
1481 (vw) 1474 (w) 1480 (s) - 1489 (vw) 1487 (m) 1486 (s) - 1505 (vw) 1593 (vw) 1511 (w) - 1508 (vw) 1498 (w sh) 1507 (w) - 1540 (vw) - 1548 (w) - 1520 (vw) 1545 (vw) 1541 (w) - 1559 (vw) - - - 1590 (vw) 1589 (m) 1587 (s) - 1616 (vw) - - - 1623 (vw) 1612 (vw) 1623 (vw) - 1634 (vw) - - - 1630 (vw) - 1645 (vw) - 1653 (vw) - - 1661 (vw) - - 1684 (vw) - - - 1674 (vw) - - - to weak - - - 2960 (vw) 2962 (vw) 2959 (vw) - to weak 3152 (vw) - - 3013 (vw) 3014 (vw) 3012 (vw) -
w weak m medium s strong v very sh shoulder a)calculated at the BP86SV(P) level b)proposed AlndashF band
78
Table E-6 includes the IR spectroscopic bands of the compounds E-1 to E-4 which are
compared to experimental and calculated values of PhndashFrarrAl(ORF)3[19] The referential wave
numbers of the almost ldquonakedrdquo [FAl(ORF)3]ndash-anion in E-4 are in good agreement to the other
compounds in the range from around 440 to 1360 cmndash1 According to the calculated bands of
Me3SindashFndashAl(ORF)3 (E-1) it was possible to assign the central AlndashF vibration which occurs at
633 and 623 cmndash1 for E-4 Unfortunately the corresponding vibrations in the other compounds
have been too weak to determine The further strong AlndashO band has been found for all
structures at 727 plusmn 2 cmndash1 which is in agreement to those found in the [Al(ORF)4]ndash-anion in
ie[33] The very intense CndashC vibrations of the C(CF3)3 groups occur at around 970 cmndash1
plusmn 2 cmndash1 For those compounds containing arene rings the CndashC and CndashH vibrations are in a
range of 890 to 1074 cmndash1 The CndashO and CndashF bands are typically for those perfluorinated
anions (cf [Al(ORF)4]ndash[33]) at 1150 to 1370 cmndash1 The band around 1252 plusmn 10 cmndash1 is an
explicit indication for a strong CndashF vibration Beyond 1370 cmndash1 it has been able to assign the
bands to current CndashC and CndashH vibrations[34] (latter 2960 and 3012 plusmn 2 cmndash1) of compounds
E-2 E-3 and E-4 Summarizing all the facts it has been possible to compare all [FAl(ORF)3]ndash
-compounds directly Most of the vibrations of comparable compounds are in good agreement
and confirm the structural properties in all salts
E4 Conclusion
Five structures containing one unity of the Lewis base anion [FAl(ORF)3]ndash as well as two
structures with fluoride bridged anions [(RFO)3AlndashFndashAl(ORF)3]ndash and
[(RFO)3AlndashFndashAl(ORF)2ndashAl(ORF)3]ndash have been characterized Useful starting materials (Ag+
[CPh3]+ and [N(Bu)4]+) and the ion-like Me3SindashFndashAl(ORF)3 (E-1) have been introduced The
free [Me3Si]+ silylium ion is a fierce electrophile making chemical stability of the counterion
a critical factor for the stabilization of compounds including the [Me3Si]δ+ moiety For
comparison the 35-bis(trifluoromethyl)-tetraphenylborate ion [B(ArF)4]ndash (ArF = 35-(RF)2-
79
C6H3 RF = n-C4F9[35] 2-C3F7
[35]) is unstable with the respect to fluoride ion abstraction in the
presence of incipient silylium ions and all anions which are themselves Lewis acidbase
adducts ([BF4]ndash [SbF6]ndash [B(OTeF5)4]ndash[36] [Sb(OTeF6)6]ndash[36] etc) are susceptible to fluoride
or oxyanion abstraction by [Me3Si]+ Based on the SindashF bond valence and compared to
Willners (as a liquid truly ionic) compound [Me3Si]+[C2H5CB11F11]ndash[29] an ionization of about
58 has been reached accounted for by the formula [Me3Si]δ+[FAl(ORF)3]δndash Hence this ion-
like compound may be considered as an electronic and structural hybrid of covalent non
interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+[FAl(ORF)3]ndash (see Scheme E-2)[6]
Me3SindashFndashAl(ORF)3 (E-1) thus is the first ion-like structure of the [FAl(ORF)3]ndash-anion This is
in agreement with the fact that [FAl(ORF)3]ndash is more stable against [SiMe3]+ than [SbF6]ndash and
that Al(ORF)3 is a stronger Lewis acid than SbF5[19] In contrast to the ion-like silylium-
carborane compounds which require a difficult multi step synthesis Me3SindashFndashAl(ORF)3 (E-
1) can be prepared in a 30 g scale per day and thus opens new synthetic possibilities The
structures of E-2 and E-3 show that the (Al)ndashF tooth is available for coordination but
depending on the nature of the counterion is a rather weak donor This is in agreement with
the notion that the Ag+ cation in E-2 and E-3 is still very electron deficient and coordinates
three arene molecules This should be contrasted by the weak capacity of the halogenated
carborane anions to stabilize Ag(arene) complexes Comparison to compound E-5[21] with a
truly ldquonakedrdquo [Ag(arene)3]+ cation and the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the [FAl(ORF)3]ndash
WCA is a good candidate to stabilize highly electrophilic cations ie as ion-like compounds
It is interesting to note many compounds that are addressed in text books as salts qualify with
respect to the bond valence to the coordinated counterion as ion-like Prominent examples
include Seppeltrsquos AuIIndashXe complexes with coordinated [SbnF5n+1]ndash anions (eg
(Xe)2Au[FSbF5]2 d(AundashFAsF5) = 216 Aring or 0651 vu) as well as many fluoroxenonium
cations (eg FndashXe[FAsF5] d(XendashFAsF5) = 214 Aring or 0685 vu) Here a large potential to
80
open new chemistry on the basis of the Lewis acids Al(ORF)3 and PhndashFrarrAl(ORF)3 as well as
the WCA [FAl(ORF)3]ndash can be seen
The reaction in Eq E-3 provides a simple one pot procedure to silver and ammonium salts of
the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash The new preparation is superior to the
older three step procedure[15 17]
Compound E-6 may be described as a doubly bridged Al(ORF)3-adduct complex of a central
[F2Al(ORF)2]ndash-anion and features analogies to the very strong Lewis acid SbF5 The
advancement from [FAl(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)3]ndash to [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash provides structural analogues to the [SbF6]ndash [Sb2F11]ndash and [Sb3F16]ndash series of
anions again highlighting the Lewis acidity of Al(ORF)3
81
References to Chapter E [1] R J Gillespie Canad Chem Ed 1969 4 9 [2] G A Olah Angew Chem Int Ed 1995 34 1393 G A Olah Angew Chem 1995 107 1519 [3] G A Olah Laali Kenneth K Wang Qi Prakash G K Surya Onium Chem
1 ed Wiley 1998 [4] P J F de Rege J A Gladysz I T Horvath Science 1997 276 776 [5] S Hollenstein T Laube J Am Chem Soc 1993 115 7240 [6] C A Reed Acc Chem Res 1998 31 325 [7] Z Xie J Manning R W Reed R Mathur P D W Boyd A Benesi C A Reed J Am Chem Soc
1996 118 2922 [8] K-C Kim A Reed Christopher W Elliott Douglas J Mueller Leonard F Tham L Lin B Lambert
Joseph Science 2002 297 825 [9] R J Gillespie J Passmore Ad Inorg Chem Radiochem 1975 17 49 [10] H Willner F Aubke Angew Chem Int Ed 1997 36 2402 H Willner F Aubke Angew Chem 1997 109 2506 [11] T Drews K Seppelt Angew Chem Int Ed 1997 36 273 T Drews K Seppelt Angew Chem 1997 109 264 [12] S Seidel C van Wuellen K Seppelt Angew Chem 2007 38 S Seidel C van Wuellen K Seppelt Angew Chem Int Ed 2007 46 6717 [13] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem 2008 in progress [14] H Schmidbaur H F Klein Angew Chem Int Ed 1966 5 726 H Schmidbaur H F Klein Angew Chem 1966 78 750 [15] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chemistry 2004 10 5041 [16] P Politzer M Levy J Chem Phys 1988 89 2590 [17] I Krossing Chem Eur J 2001 7 490 [18] J P Stewart J Mol Model 2007 13 1173 [19] L O Muumlller D Himmel J Stauffer G Steinfeld J Slattery V Brecht I Krossing Angew Chem
2008 in progress [20] J Mason Multinuclear NMR 1987 [21] L O Muumlller J Stauffer D Himmel G Santiso-Quintildeones R Scopelitti I Krossing J Am Chem
Soc 2008 submitted the compound was characterized and synthesized by G Santiso-Quintildeones and was taken into account for the comparison in this work
[22] I D Brown J Appl Crystall 1996 29 479 [23] A S Batsanov S P Crabtree J A K Howard C W Lehmann M Kilner J Organom Chem 1998
550 59 [24] Z Xie B-M Wu T C W Mak J Manning C A Reed Inorg Chem 1997 1213 [25] C-W Tsang Q Yang E T-P Sze T C W Mak D T W Chan Z Xie Inorg Chem 2000 39
5851 [26] I Krossing Chem Eur J 2001 7 490 [27] A Klamt G Schuumluumlrmann J Chem Perkin Trans 2 1993 799 [28] J B Lambert L Kania S Zhang Chem Rev 1995 95 1191 [29] H Willner Angew Chemistry 2007 119 6462 [30] B Rempfer H Oberhammer N Auner J Am Chem Soc 1986 108 3893 [31] S P Hoffmann T Kato F S Tham C A Reed Chem Comm 2006 767 [32] K Shelly D C Finster Y J Lee W R Scheidt C A Reed J Am Chem Soc 1985 107 5955 [33] I Krossing I Raabe Chem Eur J 2004 10 5017 [34] M Hesse H Meier B Zeeh Spektroskopische Methoden in der organischen Chemie 2002 [35] K Fujiki J Ichikawa H Kobayashi A Sonoda T Sonoda J Fluorine Chem 2000 102 293 [36] D M Van Seggen P K Hurlburt O P Anderson S H Strauss Inorg Chem 1995 34 3453
82
F Summary
In the first part of this thesis one of the obvious aim was the preparation of new Lithium
alkoxides of the type LiORF (RF = C(R)(CF3)2 R = tBu or mesitylene (Mes)) These alkoxides
should be applicable as precursors for the corresponding weakly coordinating aluminates
[Al(ORF)4]ndash to stabilize strongly electrophilic cations In the new WCAs the oxygen atoms
were anticipated to be better shielded than in the current [Al(ORF)4]ndash species (RF = C(CF3)3
C(H)(CF3)2 C(CH3)(CF3)2) However the chosen synthetic routes based on the reactions of
hexafluoroacetone with tBuLi or tBuMgX (X = Cl I) as suitable tBu sources did not lead to
the presumed compound LiOC(tBu)(CF3)2 The routes rather resulted in Hndash- abstraction of the
tBu unit and formation of isobutene instead of adding the tBu group to the electrophilic
carbonyl atom of (CF3)2CO The initial solvent dependant addition of Hndash to hexafluoroacetone
led to the different Lithium alkoxide [Li(OC(H)(CF3)2)]4Et2O (Fig F-1) which in THF was
able to coordinate another (CF3)2CO giving the new alkoxy-alkoxide
(THF)3LiO(CF3)2OC(H)(CF3)2 (Fig F-2)
Fig F-1 and F-2 Section of the crystal structure of [LiOC(H)(CF3)2]42Et2O (left) and molecular structure of
(THF)3LiO(CF3)2OC(H)(CF3)2 (right)
83
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
Li1
Cl1lsquo
Cl1
O1 O1lsquo
Ga1
Br1lsquoBr1 F5lsquoF4lsquo
F6lsquo
F3lsquoC1lsquo
C8lsquo
F1lsquo
F5
F2
C12
C12lsquo
DFT calculations showed that this Hndash addition was kinetically and thermodynamically
favoured However the straight forward but unexpected synthesis of
(THF)3LiO(CF3)2OC(H)(CF3)2 might be of importance for further WCA chemistry if a weak
oxygen donor is desired in the periphery of such an anion Instead of choosing the tBu-group
it was possible to fulfil the requirement for a bulky Lithium alkoxide by the synthesis with
hexafluoroacetone and Lithium mesitylene In contrast to the former mentioned
[Li(OC(H)(CF3)2)]4Et2O which crystallized in a heterocubane structure the central structure
in this Lithium mesitylene complex [LiOC(CF3)2Mes]4 was a rare puckered eight membered
ring (Fig F-3) Unfortunately the further attempted synthesis to the desired aluminate
[Al(ORF)4]ndash (RF = C(CF3)2Mes) did not lead to success The only result was the
doubleheterocubane crystal structure of Li[OC(CF3)2Mes]4[LiF]2 Another attempted route via
the congruent synthesized alcohol HOC(CF3)2Mes and LiAlH4 with various solvents did not
lead to any reaction Apparently the bulk of the C(CF3)2Mes-group is too large to allow
incorporation to the desired aluminate Similarly the respective [Ga(ORF)4]ndash could not be
prepared by the synthesis of LiOC(CF3)2Mes with GaBr3 Instead of the gallate the
disubstituted dichloroethancomplex Li(C2H4Cl2)[Ga(OC(CF3)2Mes)2(Br)2] could be isolated
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
F10lsquo F4C3
F3
C2
F1O1Li2lsquoF8lsquo
O2lsquoC13lsquo
Li1lsquo
O1lsquo
C1
Li1
Li2F2lsquo O2 C13 C16
F8
F8lsquo
C1lsquo
C3lsquoF4lsquo
C15F10lsquo
C16lsquo
C21lsquo
C21
Fig F-3 and F-4 Molecular structures of [LiOC(CF3)2Mes]4 (left) and Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2
(right)
84
The dichloroethancomplex (Fig F-4) describes the first account of a non-heterocubane Li-
Chloroalkane complex and demonstrates that the hard Li+ cation prefers coordination towards
the hard and poorly accessible oxygen atom over the soft but easily accessible bromine atoms
Summarizing all the ideas mentioned before the fluorinated alkoxy rests were to bulky to
coordinate four times the small Al-atom Even the larger Ga as central atom did not fulfil this
requirement The consequential idea was to vary the RF rest to a less bulky long-chained
Lithium alkoxid unit with RF = C(CF3)2CH2SiMe3 which was able to give the new
corresponding aluminate [Al(OC(CF3)2CH2SiMe3)4]ndash In this respect the alkoxy unit was
anticipated to be more stable than the bulky CH2SiMe3-group which shields the oxygen
atoms protects them from electrophilic attack and even induces solubility in aliphatic solvents
like n-hexane This Lithium aluminate even was able to stabilize [Ph3C]+ which may be seen
as a representative example for a strong electrophile Due to the absence of β-H atoms in the
CH2SiMe3-group it is known to be a good ligand in transition metal chemistry and Li ion
catalysis and also proves as salt with application in WCA chemistry
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Al2
O13O1
O4O12
Li2
F18
F113F118
F101F104
C117C115
Si7
Si6
Si5
Si8
F108 F122
Fig F-5 Section of the polymeric crystal structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash
85
From the first part of this thesis it is obvious that the main principle of WCAs are complex
anions which contain bulky and preferably strong Lewis acidic species In this case the
WCA [Al(ORF)4]ndash contains as the principle component the very strong Lewis acid Al(ORF)3
(RF = C(CF3)3) which is the acidic centre of the corresponding weakly coordinating
aluminate Therefore the second and main part of this thesis was focussed on the parent
Lewis acid Al(ORF)3 as its conjugated base anion [FAl(ORF)3]ndash As known from literature the
strength of a Lewis acid is defined by the fluoride ion affinity (FIA) From this point of view
Al(ORF)3 may even be seen as Lewis Superacid in comparison to classical Lewis acids
Further reactions with this acid revealed the problem of the instability of pure Al(ORF)3 due to
internal (C)ndashF activation above 273 K However a pentanehexane suspension could be used
in further reactions for the preparation of [FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash salts To
avoid this decomposition a room temperature stable alternative of this acid the
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 (Fig F-6) was synthesized which now may
be handled as stable stock solution at 298 K
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Al1O3
O1
O2
F1C1
C7
F2
C15
C11
Fig F-6 Molecular structure of PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
Proving this superacidity of PhndashFrarrAl(ORF)3 experimentally the reaction with a suitable
[SbF6]ndash source was performed and proceeded successfully with fluoride abstraction giving the
86
conjugated [FAl(ORF)3]ndash-anion Forward-looking the fluorobenzene adduct complex Phndash
FrarrAl(ORF)3 may be widely used in all applications that need high and hard Lewis acidity
In the last chapter the chemistry of the conjugated WCA [FAl(ORF)3]ndash and its increased
fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash is described The synthesis useful materials
such as Ag+ [N(Bu)4]+ and [Ph3C]+ succeeded with the WCA [FAl(ORF)3]ndash Due to the
smaller size of the Ag it tends to coordinate three aromatic solvent molecules to be
energetically saturated [Ag(arene)3]+[A]ndash (arene = toluene fluorobenzene [A]ndash =
[FAl(ORF)3]ndash and [(RFO)3AlndashFndashAl(ORF)3]ndash) The comparison of [FAl(ORF)3]ndash with a truly
ldquonakedrdquo [Ag(arene)3]+ cation to the least coordinating WCA [(RFO)3AlndashFndashAl(ORF)3]ndash
(Fig F-7) support the view that [FAl(ORF)3]ndash itself is already a good WCA Thus the
[FAl(ORF)3]ndash WCA constitutes a good candidate to stabilize highly electrophilic cations The
compound [Ph3C]+[FAl(ORF)3]ndash was a prime example for an almost ldquonakedrdquo cation weakly
coordinated by an unhindered [FAl(ORF)3]ndash-anion (Fig F-8)
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Ag2
C203C204 C214
C215
C208C207
Al3
Al4
F203
O8
O7 O9
O11
O12
O10C29
C25
C33
C41
C37
Fig F-7 Section of the crystal structure of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3)
87
Al1
O3
O1
O2
C9
C1
C5
F1Al1
O3
O1
O2
C9
C1
C5
F1
Fig F-8 Section of the crystal structure of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
All salts led to room temperature stable compounds of the weakly coordinating anion
[FAl(ORF)3]ndash which may be used for further chemistry Furthermore the synthesis of the first
ion-like structure of the [FAl(ORF)3]ndash-anion succeeded Thus the formation of
Me3SindashFndashAl(ORF)3 (Fig F-9) is in agreement with the fact that [FAl(ORF)3]ndash is more stable
against [SiMe3]+ than [SbF6]ndash and that Al(ORF)3 is a stronger Lewis acid than SbF5
O3
O2
O1Al1
F1Si1
C4C8
C12
O3
O2
O1Al1
F1Si1
C4C8
C12
Fig F-9 Section of the crystal structure of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
The free SiMe3+ silylium ion states an extraordinary strong electrophile making chemical
stability of the counterion a critical factor for the stabilization of compounds including the
88
[Me3Si]δ+ moiety Hence this ion-like compound may be considered as an electronic and
structural hybrid of covalent non interacting Me3SiFAl(ORF)3 as well as ionic [Me3Si]+
[FAl(ORF)3]ndash Similarly herein the [FAl(ORF)3]ndash WCA proves as good candidate to stabilize
the highly electrophilic compound [Me3Si]+
In brief several syntheses to new bulky Lithium alkoxides have been developed however the
synthesis of a new Lithium aluminate succeeded only by the sterical less demanding ndash
C(CF3)2CH2SiMe3 residue Furthermore the new Lewis Superacid Al(ORF)3 its corresponding
conjugated base [FAl(ORF)3]ndash and the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash could
be synthesized as Ag+ [N(Bu)4]+ salts via a new developed route Al(ORF)3 and its
fluorobenzene adduct complex PhndashFrarrAl(ORF)3 serve as potential candidates where Lewis
acidic properties are needed and [FAl(ORF)3]ndash as a counterion that tolerates maximum
electrophilicity
89
G Experimental Section
G1 General Experimental Techniques
G11 General Procedures and Starting Materials
Due to air- and moisture sensitivity of most materials all manipulations (if not mentioned
otherwise) were undertaken using standard vacuum and Schlenk techniques as well as a glove
box with an argon or nitrogen atmosphere (H2O and O2 lt 1 ppm) All solvents were dried by
conventional drying agents and distilled afterwards For some syntheses two bulbed Schlenk
vessels fitted with two Young valves and a G4 frit plate were used (see Fig G-1)
Fig G-1 Two bulbed Schlenk vessel with Young valves and G4 frit plate Measures are given in mm however
the values may differ depending on the size of the syntheses approach
G12 NMR Spectroscopy If not otherwise specified all solution NMR spectra were recorded in CD2Cl2 or [D5]PhndashF at
the temperatures given in the text on a Bruker AC 250 on a Bruker AVANCE II+ 400 and on
90
a Varian Unity 300 spectrometer data are given in ppm relative to the internal solvent signals
(1H 13C) or external FCCl3 (19F) SiMe4 (29Si) Al(H2O)63+ (27Al) and 85 H3PO4 (31P)
G13 IR and Raman Spectroscopy IR spectra were recorded at rt on a Bruker VERTEX 70 and a Bruker IFS 66v spectrometer
in Nujol mull between CsI or AgBr plates or on a Nicolet Magna 760 spectrometer using a
diamond Orbit ATR unit (extended ATR correction with refraction index 15 was used)
Raman spectra were recorded at rt on a Bruker IFS 66v and a Bruker RAM II FT-Raman
spectrometer (using a liquid nitrogen cooled highly sensitive Ge detector) in sealed NMR
tubes or melting point capillaries (1064 nm radiation 2 cmndash1 resolution)
G14 X-Ray Diffraction and Crystal Structure Determination
Data collection for X-ray structure determinations were performed on a STOE IPDS II or a
BRUKER APEX II diffractometer all using graphite-monochromated Mo-Kα (071073 Aring)
radiation Single crystals were mounted in perfluoroether oil on top of a glass fiber and then
brought into the cold stream of a low temperature device so that the oil solidified When the
crystals were grown at very low temperature or were very sensitive to temperature they were
mounted between ndash40 and ndash20degC with a cooling device All structural calculations were
performed on PCacutes using the SHELX97[1] software package The structures were solved by
the Patterson heavy atom method or direct methods and successive interpretation of the
difference Fourier maps followed by least-squares refinement All non-hydrogen atoms were
refined anisotropically The hydrogen atoms were included in the refinement in calculated
positions by a riding model using fixed isotropic parameters Occasionally the movement of
the anionic parts was restricted using SADI commands Relevant data concerning
crystallographic data data collection and refinement details are compiled in Chapter L
Crystallographic data of most compounds excluding structure factors have been deposited at
the Cambridge Crystallographic Data Centre (CCDC) The respective CCDC numbers are
91
included in Chapter X Copies of the data can be obtained free of charge on application to
CCDC 12 Union Road Cambridge CB21EZ UK (fax (+44)1223-336-033 email
depositccdccamacuk)
92
G15 Syntheses and Spectroscopic Analyses G151 Preparation of [Li(OC(H)(CF3)2]42Et2O (B-1) Approximately 30 ml n-hexane were
added to a solution of 92 ml (1562 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) Upon the
frozen mixture 311 g (1874 mmol 12 eq) hexafluoroacetone was condensed at 77 K It was
warmed up to 195 K and - with stirring over night - to room temperature Then the solvent
was removed by vacuum distillation and the resulting colorless oil (403 g) isolated and
crystallized from Et2O The structure of the colorless crystals was identified as
[Li(OC(H)(CF3)2]42Et2O (B-1) (mcrystals 125 g 48 vs hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-1) 1H NMR (400 MHz) δ = 11 (t 12H) 34 (q 8H) 441
(sep 4H) 19F NMR (376 MHz) δ = ndash75 (s 6F) 13C[1H] (100 MHz) δ = 299 (s) 533 (s)
739 (broad) 1244 (q 1JCF = 2912 Hz) 7Li NMR (155 MHz) 57 (s 1Li)
IR (CsI plates nujol) ν = 470 (w) 553 (w) 558 (w) 636 (w) 689 (s) 707 (s) 740 (s) 795
(vw) 852 (s) 890 (s) 920 (s) 959 (s) 973 (s) 1009 (w) 1087 (vs) 1199 (vs) 1260 (vs)
1289 (vs) 1374 (vs) 1450 (w) 1475 (w) 1488 (vw) cm-1
93
G152 Preparation of (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) Approximately 30 ml THF
were added to a solution of 12 ml (2045 mmol) tBuLi (c = 17 mol Lndash1 in n-hexane) The
mixture forms a yellow solution which was frozen to 77 K After condensing 408 g
(2458 mmol 12 eq) hexafluoroacetone onto the frozen mixture and warming to 195 K with
stirring the yellow color of the mixture disappeared The stirred mixture was allowed to
slowly reach room temperature After 24 hours the solvent was removed by vacuum
distillation at 298 K The resulting yellow oil (33 g) was crystallized from THF at 233 K The
structure was identified as (THF)3LiO(CF3)2OC(H)(CF3)2 (B-2) (mcrystals 135 g 40 vs
hexafluoroacetone)
The NMR spectra of these crystals and the supernatant solution are similar and indicate
complete transformation to (B-2) 1H NMR (400 MHz) δ = 185 (m 4H) 371 (m 4H) 441
(sep 1H) 19F NMR (376 MHz) δ =-762 (s 6F) ndash822 (s 6F) 7Li NMR (155 MHz) ndash38 (s
1Li) 13C[1H] (100 MHz) δ = 249 (s) 684 (s) 1226 (q 1JCF = 2922 Hz) 1229 (q 1JCF =
2918 Hz)
IR (CsI plates nujol) ν = 460 (vw) 530 (vw) 688 (w) 722 (w) 807 (vw) 878 (w) 895 (w)
920 (w) 959 (s) 1053 (s) 1103 (w) 1195 (vs) 1211 (vs) 1284 (s) 1381 (w) 1421 (w) 1459
(w) 1508 (vw) cm-1
94
G153 Preparation of (CF3)2(H)COMg2Et2O (B-4) 20 ml (40 mmol) of colorless tBuMgCl
(c = 2 mol Lndash1 in Et2O) were frozen to 77 K then 731 g (44 mmol 11 eq) hexafluoroacetone
were condensed onto the solid The mixture was allowed to slowly reach room temperature
with stirring After removal of the solvent by vacuum distillation a white precipitate formed
On the basis of the NMR-data and the mass balance the substance was assigned as
(CF3)2(H)COMgCl2Et2O (B-4) (mprecipitate 1086 g 96 )
1H NMR (400 MHz) δ = 141 (t 12H) 369 (q 8H) 538 (sept 1H) 19F NMR (376 MHz) δ
= ndash751 (s 6F) 13C[1H] (100 MHz) δ = 670 (s) 153 (s) 729 (broad) 1242 (q 1JCF = 2911
Hz)
IR (CsI plates nujol) ν = 529 (w) 645 (vw) 690 (w) 722 (w) 745 (w) 782 (w) 857 (w)
894 (w) 968 (vw) 1001 (vw) 1042 (w) 1099 (s) 1152 (s) 1188 (s) 1234 (s) 1297 (s) 1377
(vs) 1458 (vs) cm-1
95
G154 Preparation of MesndashLiOEt2 In a 500 ml two necked flask with vessel connected
with a dropping funnel and condenser 200ml of light yellow n-BuLi (0320 mmol 13 eq
16 M in n-hexane) were mixed with approximately 120 ml Et2O and stirred at 273 K Then
37 ml (0246 mmol ρ = 1301 gm Lndash1) of MesndashBr were dropped under stirring to the solution
after half of the addition the mixture turned cloudy and was allowed to reach room
temperature Then the mixture began to reflux because of its high exothermic reaction
Afterwards it was heated to the boiling point for 3 hours whereon the white precipitate
accumulated and the yellow color of the solution disappeared The flask was stored at 280 K
over night and then the white product filtered from the colorless solution The precipitate was
washed three times with n-hexane to remove excessive n-BuLi and then three times with
Et2O to remove eventually formed LiBr The resulting white product could be assigned by
NMR spectroscopic analysis to MesndashLiOEt2 (yield 3782 g 90 )
1H NMR (400 MHz [D8]toluene 298K) δ = 171 (s 3H ndashCH3 (ortho)) 183 (s toluene)
222 (s 3H ndashCH3 (para)) 239 (s 3H ndashCH3 (ortho)) 631 (s 1H) 633 (s 1H) 672 (s
toluene) 675 (s toluene) 683 (s toluene) 7Li NMR (156 MHz [D8]toluene 298K) ndash23 (s
1Li)
IR (CsI Nujol 298K) ν = 656 w 668 s 687 w 696 w sh 720 vw 727 vw 748 w 776 w
787 w sh 835 ms 857 vs 891 m 930 s 948 m sh 990 m 1007 m 1020 m 1027 m sh
1061 m 1091 m 1105 m 1119 m 1154 m 1204 s 1245 m 1304 m 1370 s 1377 s sh 1386
s sh 1347 s 1449 s 1456 s 1497 m 1507 m 1521 m 1539 m 1559 m 1578 s 1606 m
1626 m 1647 m 1653 m 1670 m 1675 m 1684 m 1700 m 1717 m 1734 m 1740 m
[cmndash1]
96
Raman (298K) 523 (40) 578 (94) 990 (41) 1158 (14) 1202 (6) 1279 (46) 1371 (31) 1381
(33) 1445 (19) 1454 (19) 1534 (12) 1580 (31) 2711 (10) 2729 (8) 2759 (6) 2857 (36
sh) 2916 (100) 2939 (63) 2964 (37 sh) 2996 (60) [()]
97
G155 Preparation of [LiOC(CF3)2Mes]4 (B-5) In a 500 ml two necked round bottom flask
connected to a dropping funnel and a gas cooler 30 g (0150 mol) colorless MesndashLiOEt2 were
dissolved in approximately 80 ml of toluene Then 3237 g (0195 mol 13 eq excess)
(CF3)2CO were condensed onto the frozen solution at 77 K The mixture was allowed to reach
213 K whereby the gas cooler was set with a cryostat to a temperature of 203 K After
stirring for 4 hours at 213 K the mixture was allowed to reach room temperature Then the
overlaying solution was decanted from the light yellow solid product This was isolated
washed with pentane recrystallized from toluene at 253 K isolated and dried by vacuum
distillation The resulting colorless product (yield 4310 g 98 ) was assigned by X-ray
diffraction and spectroscopy as [LiOC(CF3)2Mes]4
1H NMR (400 MHz [D8]toluene 298 K) δ = 174 (s 3H ndashCH3 (ortho)) 229 (s 3H ndashCH3
(para)) 250 (s 3H ndashCH3 (ortho)) 644 (s 1H) 651 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash680 (s 6F 2x ndashCF3) 7Li NMR (156 MHz [D8]toluene 298 K)
ndash79 (s 1Li)
IR (CsI plates Nujol 298 K) ν = 668 s 678 w 711 s 743 w 747 w 851 m 858 w 898 s
931 s 951 vs 968 m 1041 m 1100 s 1119 s 1142 vs 1156 vs 1175 s 1196 s 1205 s 1224
vs 1265 s 1286 s 1362 m 1375 m 1387 m 1395 m 1419 m 1436 m 1457 m 1465 m
1473 m 1489 m 1497 m 1507 m 1521 m 1540 s 1559 s 1570 m 1576 m 1616 m 1624 m
647 m 1653 s 1663 m 1670 m 1684 m 1700 m 1717 m 1734 m 1740 m sh 1751 m
1772 m 1792 m 2964 s [cmndash1]
Raman (298 K) 521 (33) 541 (55) 572 (62) 595 (29) 748 (64) 975 (19) 1103 (31) 1170
(16) 1282 (24) 1376 (36) 1385 (40) 1445 (19) 1465 (19) 1566 (14) 1613 (43) 2868 (27)
2923 (100) 2982 (52) 2995 (45) 3009 (36) 3022 (43) cmndash1 [()]
98
G156 Preparation of HOC(CF3)2Mes For the hydrolysis (no inert conditions) of 10 g
(3423 mmol) LiOC(CF3)2Mes approximately 20 ml of 2M HCl were given to the salt Then
the mixture was stirred for half an hour and afterwards the resulting alcohol separated from
the aqueous phase by adding three times about 40 ml fluorobenzene to the liquid The organic
phase turned light yellow and was then dried for three hours over about 50 g CaCl2 After
filtration and distillation (bp of HOC(CF3)2Mes 393 K 01 mbar) drying over P2O5 and
condensation the alcohol HOC(CF3)2Mes was isolated as a colorless liquid (yield 270 g
28 ) and then spectroscopically analyzed
1H NMR (400 MHz [D8]toluene 298 K) δ = 207 (3H ndashCH3 (ortho)) 247 (s 3H ndashCH3
(para)) 264 (s 3H ndashCH3 (ortho)) 277 (s 1H OndashH) 668 (s 1H) 678 (s 1H) 19F NMR
(376 MHz [D8]toluene 298 K) δ = ndash773 (s 6F 2x ndashCF3)
IR (CsI plates nujol 298 K) ν = 485 w 513 w 548 w 590 w 635 w 707 s 741 m 752 m
853 m 890 s 926 m 955 s 983 m sh 1098 m 1127 vs 1169 m 1198 vs 1238 vs 1386 w
1459 m 1486 m 1570 w 1613 m 2929 w 3537 m 3610 m [cm-1]
99
G157 Preparation of [LiOC(CF3)2Mes]4(LiF)2 (B-6) 3947 g (13510 mmol) of
[LiOC(CF3)2Mes]4 were given into a 250 ml round bottom flask connected to a dropping
funnel Then under stirring approximately 30 ml n-hexane was given to the powder at 273 K
Only half of the lithium alkoxide was soluble in the solvent Afterwards 090 g (3378 mmol)
AlBr3 was given at once to the mixture whereby it turned dark red It was refluxed for two
hours and then the dark solid decanted from the colorless solution which was isolated
concentrated and crystallized at 253 K The precipitated crystals were spectrocopically and
structurally assigned to [LiOC(CF3)2Mes]4(LiF)2 (yieldcrystals 0871 g 21 )
1H NMR (400 MHz [D8]toluene 298 K) δ = 189 (3H ndashCH3 (ortho)) 226 (s 3H CH3
(para)) 234 (s 3H CH3 (ortho)) 651 (s 1H) 658 (s 1H) 19F NMR (376 MHz
[D8]toluene 298 K) δ = ndash734 (s 24F 4x ndashCF3) (a signal for LindashF could not be detected) 7Li
(156 MHz [D8]toluene 298 K) ndash21 (s br 6Li)
IR (CsI plates Nujol 298 K) ν = 473 w 538 w 589 w 616 w 670 w 708 m 720 m 741 m
750 m 850 m 897 s 930 m 953 s 1038 m 1097 m 1128 m 1158 m 1198 s 1236 s 1263 s
1284 m sh 1329 m sh 1377 vs 1461 vvs 2975 w [cmndash1]
100
G158 Preparation of Li(C2H4Cl2)Ga(OC(CF3)2Mes)2(Br)2 (B-7) In a 250 ml two necked
round bottom flask connected to a dropping funnel 040 g (1283 mmol) GaBr3 dissolved in
approximately 1 ml toluene and were added to a solution of 150 g (5134 mmol)
LiO(CF3)2Mes in approximately 15 ml toluene at 213 K Then the mixture was slowly
warmed up to room temperature over night The solution was decanted from the precipitate
(probably LiBr 010 g 1151 mmol) concentrated and crystallized from C2H4Cl2 at 253 K
The resulting crystals were spectroscopically and structurally assigned as
Li(12Cl2C2H4)[(Mes(CF3)2CO)2GaBr2] (yieldcrystals 072 g 46 )
1H NMR (400 MHz CDCl3 298 K) δ = 222 (s 6H 2x MesndashCH3) 240 (s 6H 2x Mesndash
CH3) 260 (s 2H ndashCH2CH3) 271 (s 3H ndashCH2CH3) 337 (s 2H H2O (trace)) 372 (s 6H
2x MesndashCH3) 691 (s 2H MesndashH) 19F NMR (377 MHz CDCl3 298 K) δ = ndash695 (s 12F
2x ndashC(CF3)2Mes 7Li NMR (156 MHz 298 K) δ = ndash32 (s 1Li)
IR (CsI plates Nujol) ν = 417 w 485 w 498 w 536 m 543 m 581 m 597 w 645 w 660 w
679 m 702 s 714 s 745 m 755 m 867 s 903 s 935 s 959 s 976 w sh 1038 m 1087 vs
1130 vs 1200 vs 1217 vs 1238 vs 1251 vs 1381 w 1429 w 1485 m 1497 s 1569 w 1613
s 2973 s [cmndash1]
Raman (298 K) ν = 174 (100) 191 (96) 218 (35) 229 (29) 240 (sh 19) 283 (31) 325 (23)
315 (19) 336 (18) 347 (12) 377 (9) 400 (12) 411 (10) 545 (30) 555 (30) 575 (24) 598
(13) 649 (13) 662 (18) 703 (10) 722 (5) 755 (19) 763 (20) 980 (16) 1108 (12) 1137 (7)
1148 (12) 1210 (11) 1287 (13) 1383 (24) 1433 (9) 1470 (20) 1573 (8) 1616 (32) 2741
(5) 2761 (5) 2925 (60) 2960 (79) 2999 (40) 3008 (38) 3047 (36) cmndash1 [()]
101
G159 Preparation of LiOC(CF3)2CH2SiMe3 (C-1) 778 g (82625 mmol) of white
crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane The mixture was frozen to
77 K Afterwards 1651 g (99446 mmol 12 eq) of (CF3)2CO was condensed onto the white
solid and then warmed up slowly to 195 K with stirring using a cryostat The stirred mixture
was allowed to slowly reach room temperature After 24 hours the solvent was removed by
vacuum distillation at 298 K and a white solid product resulted and could be assigned to
LiOC(CF3)2CH2SiMe3 (isolated yield 1732 g 80 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 442 s 498 s 521 s 533 s 582 w 630 s 648 w 666 m 693
s 714 s 723 m 783 m 790 m 844 vs 941 vs 1020 vs 1067 vs 1110 s 1146 vs 1197 vs
1255 vs 1291 s 1308 s 1331 s 1375 s 1418 m 1458 w 2904 vw 2954 vw [cmndash1]
102
G1510 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) 1732 g (66569 mmol) of
LiOC(CF3)2CH2SiMe3 were under stirring at rt completely solved in about 60 ml n-hexane
Then 444 g (16649 mmol) freshly synthesized and sublimed AlBr3 was dissolved in about
30 ml of n-hexane and dropped to the lithium alkoxide solution at 273 K LiBr began
immediately to precipitate as white solid The mixture was stirred over night and allowed to
warm to rt To complete the formation of LiBr quantitatively the mixture was heated up to
313 K under reflux After filtration two thirds of the solvent were removed by vacuum
distillation and the resulting solution cooled to 253 K A light beige crystalline product
precipitated and could be assigned to the new lithium aluminate alkoxide salt
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (2) (yield 911 g 53 )
NMR data are collected in Table C-1 of Chapter C
IR (CsI plates Nujol 298 K) ν = 406 m 452 m 499 m 535 w 551 w 570 w 594 w 631 m
652 w 696 m 721 m 727 m 763 m 767 s 797 s 792 s 832 s 844 vs 852 s 865 s 873 s
940 s 945 s 1056 s 1068 s 1077 s 1083 s 1138 s 1140 s 1188 s 119 s 1252 vs 1255 vs
1316 s 1324 s 1336 s 1343 s 1375 w 1427 m 1459 vw 2903 vw 2958 vw [cmndash1] Raman
(298 K) ν = 231 (4) 336 (2) 499 (2) 586 (2) 632 (5) 694 (2) 726 (2) 767 (2) 1198 (4)
1320 (10) 1422 (15) 2061 (2) 2185 (1) 2907 (100) 2962 (57) [cm-1] ()
103
G1511 Preparation of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) in an one pot reaction The
procedure of the first step to LiOC(CF3)2CH2SiMe3 (C-1) was done analogous to the former
2 g (21240 mmol) of white crystalline LiCH2SiMe3 was dissolved in about 100 ml n-hexane
The mixture was frozen to 77 K Afterwards 427 g (25720 mmol 12 eq) of (CF3)2CO was
condensed onto the white solid and then warmed up slowly to 195 K with stirring The stirred
mixture was allowed to slowly reach room temperature After 24 hours a solution of 114 g
(4275 mmol) of freshly synthesized AlBr3 in about 15 ml n-hexane was added to the
dissolved lithium alkoxide at 273 K Spontaneously LiBr began to precipitate as white solid
The mixture was stirred over night and then warmed up to rt the further procedure was as
delineated above (yield 721 g 64 )
NMR and IR indicated a pure material
104
G1512 NMR scale reactions The NMR scale reaction of the lithium aluminate
Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) with Ph3CCl (according to Eq 4) was carried out in
07 ml CD2Cl2 at 298 K 01 g (0096 mmol) of C-2 were given to 0027 g (0096 mmol) of
Ph3CCl The formation of white insoluble LiCl salt could be observed The typical yellow
color of the dissolved trityl compound was obtained and NMR indicated complete
transformation
NMR data are collected in Table C-1 of Chapter C
105
G1513 Synthesis attempt of [H(Et2O)2]+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-4) 080 g (0767
mmol) of C-2 were dissolved in about 25 ml CH2Cl2 Then 025 ml Et2O (ex) were added and
0029 g (0805 mmol 105 eq) of HCl(g) condensed onto the mixture The mixture was
allowed to reach slowly room temperature the resulting residue was turbid liberated from
solvent and weighted (mresidue = 059 g equiv mtheoretical = 66 ) Apparently the expected
protonated diethylether adduct complex decomposed to Al(OC(CF3)2(CH2SiMe3)3 and LiCl
The obtained yield (mtheoretical = 92 ) and the observed NMR chemical shifts are in good
agreement with comparable compounds
106
G1514 Preparation of a 1-molar solution of PhndashFrarrAl(ORF)3 (RF = C(CF3)3) (D-1) From
a dropping funnel 418 ml (030 mol) HOC(CF3)3 were added dropwise under stirring at
268 K to a colorless solution of 137 ml (010 mol) of pure AlEt3 in approximately 15 ml
fluorobenzene in a 250 ml two necked Schlenk flask A reflux condenser connected to the
flask was cooled by a cryostat to 243 K to avoid leaking of the alcohol from the system
(HOndashC(CF3)3 bp 45degC is very volatile) After complete formation of ethane (measured
030 mol 660 L) the colorless mixture was canuled into a Schlenk tube at 273 K and filled up
with fluorobenzene to exactly 100 ml and stored at 253 K Already at 263 K the formation of
a crystalline product can be observed The structure of one of the colorless crystalline needles
was identified as PhndashFrarrAl(ORF)3 The NMR spectra of these crystals and the supernatant
solution are similar and indicate complete transformation to D-1 (yield of crystalline
PhndashFrarrAl(ORF)3 (D-1) 81 g 98 )
The NMR spectroscopic analysis of the crystals leads to the following results 1H NMR (300
MHz [D5]PhndashF 257 K) δ = 727 (m 5H ndashC6H5F) 19F NMR (282 MHz [D5]PhndashF 257 K) δ
= ndash755 (s 27F 3x ndashC(CF3)3) ndash1115 (s 1F free C6H5F) ndash1130 (s 1F free C6D5F) ndash144
(s 1F PhndashFrarrAl(ORF)3) 27Al NMR (78 MHz) 365 (s broad) ∆12 = 2350 Hz
107
FT-IR In the below sketched table experimental and calculated bands at the BP86SV(P)
level and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1) are given
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[55]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
108
G1515 Reaction of [BMIM]+[SbF6]ndash with PhndashFrarrAl(ORF)3 (RF = C(CF3)3) In a 100 ml
two necked Schlenk flask 05 ml (063 g 2205 mmol) of yellowish [BMIM]+[SbF6]ndash were
added to 365 g (4405 mmol) of frozen crystalline PhndashFrarrAl(ORF)3 After defrosting a beige
liquid was formed and could be partially crystallized at 275 K The obtained crystals could be
assigned to [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash by X-ray diffraction NMR IR and Raman
spectroscopy Unfortunately the quality of the structure is not good due to twinning and
disorder Spectroscopic analysis of the [BMIM]+[(RFO)3AlndashFndashAl(ORF)3]ndash-crystals (non
optimized yield 071 g 21 )
1H NMR (300 MHz [D5]PhndashF 298 K) δ = 115 (t 3H ndashCH3) 3J(H H) = 736 Hz 145 (qt
2H ndashCH2) 3J(H H) = 738 Hz 183 (tt 2H ndashCH2) 3J(H H) = 764 Hz 375 (s 1H NndashCH3)
400 (t 2H NndashCH2) 3JH H = 750 Hz 702 (s 1H BuNCndashH) 705 (s 1H MeNCndashH) 785 (s
1H NCndashHN) 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash741 (s 27F 3x C(CF3)3) ndash1129
(s 1F C6D5F) ndash1824 (s 1F (RFO)3AlndashFndashAl(ORF)3) 27Al NMR (78 MHz [D5]PhndashF
298 K) δ = 339 (s 1Al broad ∆ 12 = 3118 Hz) 424 (s 1Al small amount of [FAl(ORF)3]ndash)
IR (ATR 298 K) 451 (w) 537 (w) 568 (vw) 624 (vw) 640 (vw) 668 (vw) 726 (s) 830
(vw) 861 (vw) 969 (vs) 1179 (s) 1209 (s) 1237 (s) 1266 (w) 1300 (vw) 1353 (vw) [cmndash1]
Raman 231 (30) 279 (42) 327 (85) 374 (52) 522 (70) 574 (67) 645 (42) 778 (100) 816
(58) 910 (12) 1021 (12) 1058 (27) 1418 (24) [()]
The supernatant solution was also NMR spectroscopically characterized and could be
assigned to the by product [Sb2F11]ndash in FndashPh 19F NMR (282 MHz [D5]PhndashF 298 K) δ = ndash
741 (s 27F 3x ndashC(CF3)3) -999 (s [Sb2F11]ndash[52] weak) ndash1126 (s 1F C6H5F) ndash1131 (s 1F
C6D5F) ndash1157 (s broad [Sb2F11]ndash[52] weak) ndash1336 (s broad [Sb2F11]ndash[52] weak)
109
G1516 First Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a 100 mL flask
05 mL (394 mmol) Me3SiCl were dropped into a dry-ice cooled solution of 1075 g
(1000 mmol) Ag+[Al(ORF)4]ndash in about 15 mL CH2Cl2 The solution was stirred while
warming up to room temperature within one hour Evolution of gas (C4F8O) started around
263 K After stirring at room temperature for one hour all volatile products were removed
(001 mbar) The residue was recrystallized from CH2Cl2 to obtain colorless crystals of the
pure product (yieldprecipitate = 070 g 85 ) which were assigned to Me3SindashFndashAl(ORF)3 (E-1)
and spectroscopically analyzed The analyses were identical to those of the 2nd preparation
110
G1517 Second Preparation of Me3SindashFndashAl(ORF)3 (RF = C(CF3)3) (E-1) In a two necked
flask with reflux condenser 925 mL AlMe3 (537 mmol 2M in n-heptane) were given and
cooled to 263 K Afterwards 236 mL (1690 mmol) RFOH were dropped under stirring and
cooling to the solution Formation of white Al(ORF)3 and a complete evolution of CH4
(1690 mmol 038 L 100 ) after 3 h could be observed Then FSiMe3 (537 mmol 052 g)
was condensed onto the Lewis acid Afterwards the yellowish mixture was allowed to reach
room temperature This solution was washed with CH2Cl2 and recrystallized from it giving
Me3SindashFndashAl(ORF)3 (yieldprecipitate = 373 g 80 )
1H NMR (400 MHz CD2Cl2 298 K) δ = 044 (d (CH3)2(CH3)SindashFAl(ORF)3 1JHF = 127 Hz)
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash771 (s ndashC(CF3)3) ndash1561 (s broad AlndashFndashSi)
27Al (104 MHz CD2Cl2 298 K) δ = 396 (s Al ∆12 = 960 Hz) 13C[1H] (100 MHz CD2Cl2
298 K) 804 (sept ndashC(CF3)3 broad) 1220 (q ndashCF3 1JCF = 289 Hz) 05 (s ndashMe3Si)
The IR data is given in Chapter E3 Table E-6
111
G1518 Preparation of Ag+[FAl(ORF)3]ndash (recrystallized from toluene to
[Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-2)) In a two necked flask connected with a
condenser (cooled with a cryostat to 253 K) 851 mL AlMe3 (1695 mmol 2M in n-heptane)
were given in approximately 20 mL n-pentane and then cooled to 263 K Afterwards 708 mL
(5084 mmol) RFOH were dropped under stirring to the solution Formation of white
Al(ORF)3 and a complete evolution of CH4 (5084 mmol 114 L 100 ) could be observed
Finally 330 g (1695 mmol) AgBF4 were added at once to the mixture at 263 K The
formation of gaseous BF3 was quantitative (1695 mmol 038 L 100 ) Then the solvent
was removed and the slightly beige precipitate was isolated (yieldprecipitate 1353 g 93 ) It
has been recrystallized from toluene at 280 K and the resulting crystals were assigned as
Ag(tol)3+[FAl(ORF)3]ndash (2) 1H NMR (400 MHz CD2Cl2 298 K) δ = 209 (s ndashCH3) 698 (s 5x
CndashH broad) 19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1468 (s broad
AlndashF) ndash1855 (s broad AlndashFndashAl) (contaminated with lt 1 Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash)
27Al (104 MHz CD2Cl2 298 K) δ = 368 (d AlndashF 1JAlF = 470 Hz) 27Al (104 MHz CD2Cl2
243 K) 411 13C (100 MHz CD2Cl2 298 K) δ = 301 (s CH3) 804 (sept ndashC(CF3)3 broad)
1213 (s ndashCH) 1232 (s ndashCH) 1222 (q ndashCF3 1JCF = 290 Hz) 1266 (s ndashCH) 1342
(s ndashCndashCH3)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 230 (58) 247 (54) 298 (50) 329 (100) 303 (46) 372 (38) 540 (29) 572
(16) 748 (54) 753 (92) 773 (46) [()] (The vibrational bands beyond 800 cmndash1 up to 3200
cmndash1 have been to weak to assign)
112
G1519 Preparation of [Ag(FndashPh)3]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-3) In a two necked
flask with condenser (cooled with a cryostat to 253 K) 019 mL (141 mmol) AlEt3 were
given to about 15 mL of FndashPh and then cooled to 253 K Afterwards 060 mL (424 mmol)
RFOH were dropped under stirring to the solution The formation of CH4 was quantitative
(424 mmol 009 L 100 ) Finally 022 g (141 mmol) AgBF4 were added to the mixture at
once The resulting formation of BF3 was quantitative as well (019 mmol 421 mL 100 )
Then the solution was concentrated to about 60 colorless crystals formed at 253 K and
were isolated (yieldcrystals 135 g 90 )
1H NMR (400 MHz CD2Cl2 257 K) δ = 707 (m 6H ndashC6H5F) 716 (m 6H ndashC6H5F) 738
(m 3H ndashC6H5F) 19F NMR (376 MHz CD2Cl2 257 K) δ = ndash759 (s 27F 3x ndashC(CF3)3) ndash
1136 (s 3F C6H5F) ndash1471 (s 1F AlndashF) 13C NMR (100 MHz CD2Cl2 257 K) δ = 877
(m br ndashC(CF3)3) 1155 (PhndashF) 1227 q (3C ndashC(CF3)3 1JCF = 2923 Hz) 1234 (PhndashF)
1299 (PhndashF) 1628 (PhndashF) 27Al (104 MHz 257K) δ = 402 (s broad AlndashF)
The IR data is given in Chapter E3 Table E-6
FTndashRaman υ = 519 (13) 538 (16) 565 (13) 570 (13) 612 (21) 712 (16) 756 (46) 810 (76)
843 (23) 859 (27) 906 (20) 968 (19) 984 (15) 1001 (100) 1016 (27) 1034 (19) 1083 (20)
1140 (19) 1158 (30) 1237 (26) 1389 (16) 1598 (29) 1611 (24) 3083 (16) [()] (The
vibrational bands between 1600 and 3083 cmndash1 have been to weak to assign)
113
G1520 Preparation of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) About 20 mL n-pentane was
given into a two necked flask Then 140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol
Lndash1) were added to the solvent under stirring The solution was cooled to 273 K and 118 mL
(847 mmol) perfluorinated alcohol RFOH was added dropwise Al(ORF)3 begun to form and
after a complete evolution of CH4 (190 mL 100 ) 093 g (282 mmol) of [N(Bu)4]+[BF4]ndash
were given to the mixture at once Then BF3 formed quantitatively (62 mL 100 ) the
solvent was removed by vacuum distillation (10ndash2 mbar 298 K) and the remaining solid
product was isolated and assigned to [N(Bu)4]+[FAl(ORF)3]ndash (yieldprecipitate 239 g 85 ) The
product also was recrystallized from n-pentane but unfortunately the x-ray structure
[N(Bu)4]+[FAl(ORF)3]ndash (yieldcrystals 113 g 40 ) is only preliminary and the structure is only
deposited in Chapter J
1H NMR (400 MHz CD2Cl2 273 K) δ = 012 (m (ndashC4H9)4+ 095 (m (ndashC4H9)4
+) 146 (m (ndash
C4H9)4+) 305 (m (ndashC4H9)4
+) 13C (100 MHz CD2Cl2 273 K) δ = 132 (s (ndashC4H9)4+) 196
(s (ndashC4H9)4+) 239 (s (ndashC4H9)4
+) 589 (s (ndashC4H9)4+) 709 (m br ndashOC(CF3)3)) 1216 (q ndash
OC(CF3)3 1JCF = 2916 Hz) 27Al (104 MHz CD2Cl2 273 K) δ = 420 (s broad AlndashF ∆12 =
38 Hz)
The FTndashIR spectrum led to the following wave numbers 445 (ms) 489 (vw) 522 (w) 537
(ms) 562 (ms) 571 (w) 668 (ms) 726 (vs) 755 (w) 767 (ms) 798 (vw) 820 (ms) 830 (ms)
896 (w) 975 (vs) 1027 (s) 1061 (ms) 1099 (ms) 1155 (vs) 1163 (vs) 1170 (vs) 1191 (vs)
1207 (vs) 1248 (vs) 1264 (vs) 1351 (vs) 1363 (vs) 1371 (vs) 1383 (vs) 1452 (vs sh)
1456 (vs) 1471 (vs) 1538 (vs) 2881 (w) 2931 (w) 2973 (w) [cm-1]
114
G1521 Preparation of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) In a two necked flask
140 mL (282 mmol) AlMe3 (in n-heptane c = 2 mol Lndash1) were added to about 20 mL
n-pentane Afterwards 118 mL (847 mmol) RFOH were added dropwise Al(ORF)3 begun to
form and after a quantitative formation of CH4 (190 mL 100 ) 028 g (141 mmol) of
Ag+[BF4]ndash were given to the mixture at once BF3 formed quantitatively (31 mL 100 )
Then the solvent was completely removed and the resulting beige precipitate was assigned to
Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash (yield 194 g 86 )
Since the structure of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash is known from the literature[2] no
spectroscopic analyses have been undertaken
115
G1522 Preparation of [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3) (E-4) 032 g (116 mmol)
[Ph3C]+Clndash and 100 g (116 mmol) of Ag+[FAl(ORF)3]ndash were put into one side of a two
bulbed Schlenk vessel 6 mL of CH2Cl2 were put into the other side and cooled down to
243 K Then the solvent was given at once to the substances whereon the reaction was
initialized Under stirring the brownyellow mixture was held at 243 K for 25 h Afterwards
the CH2Cl2 was condensed onto the other side in order to precipitate AgCl quantitatively
Then the pure solvent was filled back to the reaction side afterwards transferred back as
brown solution onto the product side and concentrated for crystallization The crystals (yield
091 g (79 )) were identified as [Ph3C]+[FAl(ORF)3]ndash NMR of the solution shows the
reaction to be quantitative with no visible side products
1H NMR (400 MHz CD2Cl2 298 K) δ = 752 (d 3x (2x ndashCH (ring o))) 3JHH = 677 Hz δ =
782 (t 3x (2x ndashCH (ring m))) 3JHH = 677 Hz δ = 819 (t 3x ndashCH (ring p)) 3JHH = 677 Hz
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash758 (s ndashC(CF3)3) ndash1477 (s broad AlndashF) 27Al
(104 MHz CD2Cl2 298 K) δ = 384 (s broad AlndashF) 13C (100 MHz CD2Cl2 298 K) 804
(sept ndashC(CF3)3 broad) 1233 (q ndashCF3 1JCF = 290 Hz) 1324 (s Ph) 1417 (s Ph) 1444 (s
Ph) 1452 (s Ph) 2119 (Ph3C+) FTndashRaman υ = 3071 (7) 1603 (6) 1598 (45) 1588 (100)
1487 (17) 1361 (31) 1310 (8) 1307 (8) 1187 (22) 1169 (9) 1028 (14) 1000 (23) 954 (6)
918 (14) 844 (6) 770 (6) 711 (9) 625 (11) 470 (9) 404 (17) 285 (20) 235 (5) 133 (9)
[()]
116
G1523 Preparation of [Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-5)
In a 50 mL flask about 1 g (054 mmol) of Ag+[(RFO)3AlndashFndashAl(ORF)3]ndash was dissolved in
approximately 5 mL 12ndashF2Ph Then the light brown solution was concentrated and slowly
cooled down to 253 K The resulting colorless platelet crystals were assigned to
[Ag(12ndashF2C6H4)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (E-5) (yieldcrystals 091 g 87 )
19F NMR (376 MHz [D8]toluene 298 K) δ = ndash761 (s 2x (ndashC(CF3)3)3) 54F) ndash1399 (s 12ndash
F2Ph 2F) ndash1850 (s AlndashFndashAl 1F) 27Al (104 MHz [D8]toluene 298 K) δ = 344
(s AlndashFndashAl 2Al broad)
FTndashIR ν = 449 (m) 537 (m) 567 (w) 637 (w) 725 (vs) 763 (w) 802 (m) 851 (w) 866 (w)
969 (vs) 1010 (vw) 1097 (w) 1177 (s) 1209 (s) 1266 (s) 1300 (m) 1356 (w) 1460 (vw)
1508 (w) 1551 (vw) 1588 (vw) 2963 (vw) 3014 (vw) [cm-1]
No qualitatively good enough Raman spectrum could be observed
Then the flask with the material was evacuated for 5 days a small amount of the remaining
light brown powder was dissolved in CD2Cl2 for 19F NMR spectroscopic analysis to
determine the quantity of coordinated solvent molecules
19F NMR (376 MHz CD2Cl2 298 K) δ = ndash739 ppm (s 2x (ndashC(CF3)3)3) 54F) ndash1375 ppm (s
12ndashF2Ph 2F) ndash1829 ppm (s AlndashFndashAl 1F) 27Al (104 MHz CD2Cl2 298 K) δ = 370 (s
AlndashFndashAl 2Al broad) The integration led to a 19F ratio of 54408 which shows that two
solvent molecules remain coordinated
117
G1524 Synthesis attempt of [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)3]ndash giving
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) (E-6) In a two necked
flask connected with a condenser (cooled with a cryostat to 253 K) 14 mL AlMe3 (282
mmol 2M in n-heptane) were given to approximately 30 mL n-heptane and then cooled to
273 K 118 mL (847 mmol) RFOH were dropped to the mixture under stirring After the
complete evolution of CH4 (006 l 100 ) 0464 g (1141 mmol) of white [N(Bu)4]+[BF4]ndash
(dissolved in about 5 mL CH2Cl2) were added to the solution Immediately a yellow
suspension over white precipitate formed After the quantitative evolution of BF3 (31 mL 100
) the mixture was stirred for a further hour and refluxed for several hours Then the solvent
was totally removed by vacuum distillation (001 mbar) and the resulting yellowish oily solid
recrystallized from CH2Cl2 At 253 K light brown crystals of
[N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (E-6) formed (yieldcrystals 1891g 60 )
1H NMR (250 MHz CD2Cl2 298 K) δ = 013 (m N(C4H9+)) 136 (m N(C4H9
+)) 149 (m
N(C4H9+)) δ = 303 (m N(C4H9
+)) 13C NMR (63 MHz CD2Cl2 298 K) δ = 133 (s
N(C4H9+)) 199 (s N(C4H9
+)) 241 (s N(C4H9+)) 594 (s N(C4H9
+)) 1209 (q ndashOC(CF3)3
1JCF = 291 Hz1)) 1219 (q ndashOC(CF3)3 1JCF = 290 Hz2)) 1208 (q ndashOC(CF3)3
1JCF = 290 Hz3))
(1)-3) are explained by the different types of ndashC(CF3)3 groups cf the below sketched Fig X-1)
Al
RFO
RFO
RFOF
Al
RFO ORF
FAl
ORF
ORF
ORF
1 type
2 type2 type
3 type 3 type
Fig G-1 Different types1)-3) of 13C resonances of the RF = C(CF3)3 groups in [(RFO)3AlndashFndashAl(ORF)2ndashFndash
Al(ORF)3]- with intensity ratio of 242
118
IR (CsI plates nujol) υ = 451 (m) 512 (w) 537 (m) 568 (m) 647 (w) 725 (s) 740 (vw)
760 (vw) 831 (vw) 865 (w) 897 (vw) 970 (vs) 1024 (vw) 1063 (vw) 1111 (vw) 1176 (m)
1213 (vs) 1240 (s) 1300 (m sh) 1355 (w) 1462 (vw) 1484 (vw) 2885 (vw) 2939 (vw)
2978 (vw) [cm-1]
119
H Theoretical Section
H1 Frequency Calculations Thermal Corrections and Solvation Energies
Vibrational frequencies were calculated with AOFORCE[3] at the (RI-)BP86SV(P) level[4 5]
(if not specified otherwise) They were used to verify if the obtained geometry represents a
true minimum on the potential energy surface (PES) as well as to determine the zero point
vibrational energy (ZPE) Based on these frequency analyses the thermal contributions to the
enthalpy and Gibbs free energy have been calculated using the module FREEH implemented
in TURBOMOLE Calculations of solvation energies (solvents CH2Cl2 with εr(298K) = 893
and n-hexane εr(298 K and 343 K) = 19) have been done with the COSMO[6 7] module as
(RI-)BP86SV(P) single points Non-relativistic NMR shifts have been performed with the
MPSHIFT[8 9] module included in TURBOMOLE as single point calculations on converged
geometries
120
H2 Lattice Energy Calculations
Gibbs lattice energies for the Born Haber Fajans cycle have been calculated using a molecular
volume based modified Kapustinskii equation as introduced by Jenkins and Glasser[10-13]
⎟⎟⎠
⎞⎜⎜⎝
⎛β+
α= minus+
31
mpot V
zzU
α = 1173 kJ nm mol-1 β = 519 kJ mol-1
Similarly the entropy was calculated according to Jenkins and Glasser[14]
ckVS m +=
k = 1360 J (nm3 K mol)-1 s = 15 J (K mol)-1
However the calculated S are absolute entropies Thus the entropies of the gaseous
compounds have to be subtracted
LattGas SSdS minus=
In the last step the Gibbs lattice energy was calculated according to standard thermodynamic
equations
TdSRT2UTdSdHdG pot minus+=minus=
121
References to Chapter H
[1] G M Sheldrick 1997 [2] A Bihlmeier M Gonsior I Raabe N Trapp I Krossing Chem Eur J 2004 10 5041 [3] P Deglmann F Furche R Ahlrichs Chem Phys Lett 2002 362 511 [4] M Levy J P Perdew J Chem Phys 1986 84 4519 [5] A D Becke Phys Rev A At Mol Opt Phys 1988 38 3098 [6] A Klamt G Schueuermann J Chem Soc Perkin Trans 2 Phys Org Chem 1993 799 [7] A Schafer A Klamt D Sattel J C W Lohrenz F Eckert Phys Chem Chem Phys 2000 2 2187 [8] M Haeser R Ahlrichs H P Baron P Weis H Horn Theo Chim Acta 1992 83 455 [9] G Schreckenbach T Ziegler J Phys Chem 1995 99 606 [10] H D B Jenkins H K Roobottom J Passmore L Glasser Inorg Chem 1999 38 3609 [11] L Glasser H D B Jenkins Chem Soc Rev 2005 34 866 [12] H D B Jenkins J F Liebman Inorg Chem 2005 44 6359 [13] H D B Jenkins L Glasser Inorg Chem 2006 45 1754 [14] H D B Jenkins L Glasser Inorg Chem 2003 42 8702
122
I Appendix I1 Numbering of the compounds Number Compound B-1 [Li(OC(H)(CF3)2]42Et2O B-2 (THF)3LiO(CF3)2OC(H)(CF3)2 B-3 MgI22Et2O B-4 (CF3)2(H)COMgCl2Et2O B-5 [LiOC(CF3)2Mes]4 B-6 [LiOC(CF3)2Mes]4[LiF]2 B-7 Li(C2H4Cl2)[Ga(OC(CF3)2Mes(Br)2] C-1 Li[Al(OC(CF3)2(CH2SiMe3))4]
D-1 PhndashFrarrAl(ORF)3 (RF = C(CF3)3)
E-1 Me3SindashFndashAl(ORF)3 (RF = C(CF3)3)
E-2 [Ag(tol)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-3 [Ag(PhndashF)3]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-4 [Ph3C]+[FAl(ORF)3]ndash (RF = C(CF3)3)
E-5 [Ag(12ndashF2Ph)3]+[(RFO)3AlndashFndashAl(ORF)3]ndash (RF = C(CF3)3) E-6 [N(Bu)4]+[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash (RF = C(CF3)3) Fig J-AE6 [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3)
123
J Appendix
J1 Appendix to Chapter C
Table AC-1 Comparison between the wavelengths of Li+[Al(OC(CF3)2(CH2)Si(CH3)3)4]ndash (2) and
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] vibrational assignment and Raman data of C-2 values are given in [cmndash1]
Li+[Al(OC(CH3)(CF3)2)4]ndash[1] wave n [cmndash1] (intensity)
IR of C-2 wave n [cmndash1] (intensity) Assignment Raman of C-2 [cmndash1]
(intensity in ) - 231 (4) - - 336 (2)
406 vw 406 m - 443 vw 452 vw sh 452 m CndashC CndashO -
- 499 m 499 (2) - 535 w CndashC CndashO -
552 w sh 551 w CndashC AlndashO - 571 w 570 w CndashC CndashO -
- 594 w 586 (2) 622 w sh 632 w 631 m 632 (5)
- 652 w - 702 m 696 m 694 (2) 722 w 721 m - 738 w 727 m CndashC CndashO 726 (2) 773 w 763 m CndashC CndashO -
- 767 s 767 (2) 791 w 792 s -
- 832 s CndashC AlndashO - - 844 vs - - 852 s -
869 w 865 s - - 873 s - - 940 s CndashC CndashF -
980 w 993 w 1005 w 945 s CndashC CndashF - - 1056 s - - 1068 s - - 1077 s -
1088 vs 1083 s - 1121 s 1138 s -
- 1140 s - 1174 s 1188 s -
1196 vs sh 1194 s 1198 (4) 1223 vs 1252 vs CndashC CndashF - 1257 ms 1255 vs CndashC CndashF - 1312 s 1316 s -
- 1324 s 1320 (10) - 1336 s - - 1343 s -
1378 m 1375 w CndashC CndashF - - 1427 m δ(CndashH) 1422 (15)
1450 s 1458 s 1463 s 1459 vw δ(CndashH) - 1624 w - δ(CndashH) - 1781 w - δ(CndashH) -
2724 vw - δ(CndashH) - 2854 vs - δ(CndashH) - 2922 vs 2903 vw δ(CndashH) 2907 (100) 2960 vs 2958 vw δ(CndashH) 2962 (57)
wave n wave number vw very weak w weak m medium ms medium strong s strong vs very strong sh shoulder
124
Al
F
C
OLi
Si
Al
F
C
OLi
Si
Fig AC-1 Section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2)
Fig AC-2 Enlarged section of the polymeric structure of Li+[Al(OC(CF3)2(CH2SiMe3))4]ndash (C-2) arrows mark the coordinating F-atoms to the next structural unit
125
J2 Appendix to Chapter D
05 Al2X6 (g) AlX3 (s)
AlX3 (g)
∆dissH63 (Cl)59 (Br)50 (I)
∆sublH
62 (Cl)42 (Br)56 (I)
KZ(Al) = 6KZ(Al) = 4KZ(Al) = 4
[in kJ molndash1]
=gt FIA(AlX3(s)) = FIA(AlX3(g)) ndash ∆sublH ndash ∆dissH
Scheme AD-1 to derive the FIA of solid AlX3
All enthalpies were taken from the NIST webbook at httpwebbooknistgovchemistry
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
-20120 100 80 60 40 20 0 ppm
Al-signal from probehead
Fig AD-1 27Al NMR spectrum of product D-1 taken at 298 K in [D5]PhndashF
126
Fig AD-2 19F-NMR spectrum of product D-1 recorded at 298 K in [D5]PhndashF
Fig AD-3 IR spectrum of PhndashFrarrAl(ORF)3 (D-1) the most important wavelengths are assigned to the different
atom vibrations in the attached S-Table 1 which were calculated at the BP86SV(P) level
127
Table AD-1 Experimental and calculated bands at the BP86SV(P) level
and the assigned vibrations of PhndashFrarrAl(ORF)3 (D-1)
Wavelength [cmndash1] (exp)
Wavelength [cmndash1] (calc)
Vibration[2]
455 466 δas(AlndashOndashC) 537 528 δas(CndashF) 574 578 νs(OndashC) 583 594 νs(CndashC) 668 676 γs(CndashC) 726 727 νs(OndashAl) 746 743 γs(CndashF)ring 846 865 νas(OndashC)
889 894 νas(CndashOndashAl) + γas(CndashH)ring
913 903 γas(CndashH)ring 971 969 δas(CndashC)
1017 1015 νs(CndashC)ring 1074 1062 νas(CndashC)ring 1153 1158 νas(CndashF) 1183 1180 νas(CndashF) 1212 1213 δs(CndashC) 1301 1308 νas(OndashC) 1358 1354 νs(OndashC)
Explanation of the abbreviations in Table 1 ν = vibrational δ = deformation γ = out of plane s = symmetric as = antisymmetric
-50 -100 -150 ppm-50 -100 -150 ppm
Fig AD-4 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF
128
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
-100 -110 -120 -130 -140 -150 ppm
-1157-999 -1336
ppm Fig AD-5 Representative enlarged section of the 19F NMR spectrum of the reaction of PhndashFrarrAl(ORF)3 and
[BMIM]+[SbF6]ndash taken at 298 K in [D5]PhndashF Arrows indicate the position of the [Sb2F11]ndash lines
129
J3 Appendix to Chapter E
-7444
-11348 -11407 -18388
Fig AE-1 19F NMR spectrum of [BMIM]+[(RFO)3AlndashFndashAl(ORF)3] (cf Chapter E Eq E-5) taken in [D5]PhndashF
at 298 K The most important peaks are given in the figure It demonstrates the typical signal at about ndash74 ppm
which belongs to the equivalent CF3 groups in the [FAl(ORF)3]ndashndashanion The signals at ndash113 ppm and ndash114 ppm
are significant for PhndashF and (C6D5F) The most important peak appears at about ndash184 ppm which proves the
formation of the fluoride bridged anion [(RFO)3AlndashFndashAl(ORF)3]ndash
130
Fig AE-3 and Fig AE-4 HindashResESI spectra of Ag+[FAl(ORF)3]ndash (left) and [N(Bu)4]+[FAl(ORF)3]ndash
(right) showing the dismutation and formation of the homoleptic [Al(ORF)4]ndash anion over time
131
Fig AE-5 Section of the structure of the trimeric (FAl(ORF)2)3 (the core with the most important atom labels is
given on the right)[3]
N Al
OC
F
C
N Al
OC
F
C
Fig AE-6 Section of the crystal structure of [N(Bu)4]+[FAl(ORF)3]ndash (RF = C(CF3)3) (3) at 150 K with thermal
displacement ellipsoids showing 50 probability
132
References to Chapter J3
[1] I Krossing Chem Eur J 2001 7 490 [2] According to the calculated vibrational frequencies at the BP86SV(P) level the vibrations of B-1 could
be directly assigned [3] N Trapp diploma thesis 2004 unpublished
133
K Computational data of all calculated species Table K-1 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 189 for n-hexane) at the BP86SVP level of all calculated structures in Chapter B
Compound U ZPE Hdeg Gdeg COSMO
(tBuLi)4 ndash15763944 010865 29996 21094 029781 (F3C)2CO ndash78803268 003739 12199 057 040745
(F3C)2(tBu)COLi ndash94580034 015423 44304 29746 048853 (F3C)2(H)COLi ndash78867642 004569 14406 2271 040722 (CH3)2CCH2 ndash15709294 010425 28794 19919 029781
134
Table K-2 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
at 298 K as well as COSMO solvation enthalpies (εr = 548 for PhndashF) at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO PhndashF ndash33124682 008998 25002 15954 ndash000296
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497
[FAl(ORF)3]ndash ndash371887769 016590 54969 21300 ndash004150
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 033091 109621 49434 ndash003186
Al(ORF)3 ndash361891753 016446 54066 22470 ndash000244 SbF5 ndash50434073 001035 4707 ndash5870 ndash000875
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081
OCF3ndash ndash41263728 - - - -
OCF2 ndash31280302 - - - - AuF5 ndash63446968 - - - -
AuF6ndash ndash73443545 - - - -
Al(C6F5)3 ndash242431623 - - - -
[FAl(C6F5)3]ndash ndash252427283 - - - - AlI3 ndash27693301 - - - -
[FAlI3]ndash ndash37689046 - - - - AlBr3 ndash796498011 - - - -
[FAlBr3]ndash ndash806492787 - - - -
135
Table K-3 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO B2(C6F5)(C6F4)2 ndash275939542 - - - -
[FB2(C6F5(C6F4)2]ndash ndash285932942 - - - - B(C10F7)3 ndash408936603 - - - -
[FB(C10F7)3]ndash ndash418931234 - - - - AlF3 ndash54188983 - - - -
[FAlF3]ndash ndash64182254 - - - - AlCl3 ndash162290465 - - - -
[FAlCl3]ndash ndash172284767 - - - - GaI3 ndash195942418 - - - -
[FGaI3]ndash ndash205935145 - - - - BI3 ndash5927797 - - - -
[FBI3]ndash ndash15921957 - - - - B(C12F9)3 ndash408936603 - - - -
[FB(C12F9)3]ndash ndash418931234 - - - - Ga(C6F5)3 ndash410680716 - - - -
[FGa(C6F5)3]- ndash420673237 - - - - B(C6F5)3 ndash220675297 - - - -
[FB(C6F5)3]ndash ndash230667671 - - - - GaBr3 ndash964745623 - - - -
[FGaBr3]ndash ndash974737654 - - - -
136
Table K-4 Total energies U [au] at the BP86SVP level of all calculated structures in Chapter D
Compound U ZPE Hdeg Gdeg COSMO BBr3 ndash774733631 - - - -
[FBBr3]ndash ndash784725801 - - - - GaCl3 ndash330536839 - - - -
[FGaCl3]- ndash340528714 - - - - GaF3 ndash222430029 - - - -
[FGaF3]ndash ndash232421882 - - - - BCl3 ndash140527457 - - - -
[FBCl3]ndash ndash150518222 - - - - OCndashB(CF3)3 ndash115029660 - - - -
[FB(CF3)3]ndash ndash113697515 - - - -
137
Table K-5 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
PhndashF ndash33124682 008998 25002 15954 ndash000296i)
PhndashFrarrAl(ORF)3 ndash395017753 025560 79949 42918 ndash000497i)
[SbF6]ndash ndash60428148 001246 5312 ndash5631 ndash006269i)
[Sb2F11]ndash ndash110868393 002389 10766 ndash6344 ndash005081i)
[FAl(ORF)3]ndash ndash371887769 017179 54969 21300 ndash004150i)ndash005074ii)
[FAl(ORF)3]ndash ndash371887769 017179 9111iv) 6996iv) ndash001966iii)
[FAl(ORF)3]ndash ndash371887769 017179 7081v) 4990v) ndash001966iii)
PF5 ndash84024920 001603 5458 ndash3680 ndash006780i)
PF6ndash ndash94015393 001887 6588 ndash2466 ndash006780i)
[(FAl(ORF)3)2]2ndash ndash743768485 033201 110142 51490 ndash013876ii)
[Al(ORF)4]ndash ndash474455051 022593 71955 31518 ndash004041ii)
[Al(ORF)4]ndash ndash474455051 022593 11700iv) 9000iv) ndash001330iii)
[Al(ORF)4]ndash ndash474455051 022593 9189v) 6427v) ndash001330iii)
[F2Al(ORF)2]ndash ndash269319805 017022 37951 11933 ndash005590ii)
[F2Al(ORF)2]ndash ndash269319805 017022 6061iv) 4642iv) ndash001227iii)
[F2Al(ORF)2]ndash ndash269319805 017022 4712v) 3296v) ndash001227iii)
138
Table K-6 Total energies U [au] ZPE (= zero point energy) [au] thermal contributions to enthalpy and gibbs free energy [kJ molndash1]
as well as COSMO solvation enthalpies at the BP86SVP level of all calculated structures in Chapter E
Compound U ZPE Hdeg Gdeg COSMO
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 17793iv) 13396iv) ndash001001iii)
[(RFO)3AlndashFndashAl(ORF)3]ndash ndash733785243 034247 13846v) 9539v) ndash001001iii)
Al(ORF)3 ndash361891753 011802 8362iv) 5834iv) ndash000954iii)
Al(ORF)3 ndash361891753 011802 6490v) 4503v) ndash000954iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 24704iv) 13515iv) ndash00238iii)
[(RFO)3AlndashFndashAl(ORF)2ndashFndashAl(ORF)3]ndash ndash993111593 046322 14024v) 9618v) ndash00238iii) FSiMe3 ndash50892757 011011 - - -
Me3SindashFndashAl(ORF)3 ndash41278800 027593 - ndash901 ndash00065ii)
[SO3CF3]ndash ndash96104280 002598 - ndash19459 ndash007712ii) Me3SindashOndashSO2CF3 ndash137010623 013575 - ndash884 ndash000638ii) Footnotes for Table J-5 and J-6 i)εr = 548 (for PhndashF) at 298 K ii)εr = 893 (for CH2Cl2) at 298 K iii)εr = 1850 (for nndashhexane) iv)calculated at the PM6 level at 343 K v)calculated at the PM6 level at 298 K
139
L Crystal Structure Tables Table L-1
Compound [Li(ORF)]42Et2O (THF)3LiO(CF3)2ORF [LiORF]4
RF = helliphellip C(H)(CF3)2 (B-1) C(H)(CF3)2 (B-2) C(CF3)2Mes (B-5) CCDC-Number 293664 293665 655229
Empirical Formula C20H24F24Li4O6 C18H25F12LiO5 C48H44F24Li4O4 Crystal Size [mm3] 033 x 019 x 011 017 x 015 x 010 029 x 022 x 015
Crystal System Monoclinic Monoclinic Orthorombic Space Group P21n P21n Pbcn
a [Aring] 107940(12) 96874(15) 111781(8) b [Aring] 33443(4) 168076(19) 153994(7) c [Aring] 190211(16) 150706(17) 284597(13) α [deg] 90 90 90 β [deg] 10639(3) 90477(11) 90 γ [deg] 90 90 90
V [Aring3] 67306(12) 24537(6) 48989(5) Z 8 4 4
ρ(calc) [Mg mndash3] 1666 1506 1584 micro [mmndash1] 0200 0164 0160
Absorption Correction 07809 08122 Tmin Tmax 12050 12294
F(000) 3360 1136 2368 ndash12 le H le 12 ndash10 le H le 11 ndash12 le H le 11
Index Ranges ndash39 le K le 39 ndash19 le K le 20 ndash18 le K le 18 ndash21 le L le 19 ndash17 le L le 17 ndash33 le L le 33
2θrange [deg] 272 to 2503 321 to 2503 301 to 2503 Temperature [K] 140 140 140
Reflections Collected 38871 13843 28669 Reflections Unique 11239 4207 4216
Parameters 973 326 361 GOOF 1124 1114 1124
Final R wR2 (2σ) 01064 03207 00815 02451 00835 01954 Final R wR2 (all) 01648 03658 01243 02718 01130 02178
Large Res Peak [e Aringndash3] 1011 0515 0489
140
Table L-2
Compound [LiORF]4(LiF)2 Li(EtCl2)Ga(ORF)(Br)2 Li[Al(ORF)4]
RF = helliphellip C(CF3)2Mes (B-6) C(CF3)2Mes (B-7) (CF3)2(CH2SiMe3) (C-1) CCDC-Number 655228 655230 661685
Empirical Formula C48H44F26Li6O4 C26H26Br2Cl2F12GaLiO2 C31H44AlF24LiO4Si4 Crystal Size [mm3] 030 x 026 x 022 026 x 022 x 020 01 x 01 x 02
Crystal System Monoclinic Tetragonal Monoclinic Space Group P21c P41212 P21c
a [Aring] 147855(10) 111582(10) 25079(5) b [Aring] 118441(7) 111582(10) 14115(3) c [Aring] 146062(10) 261495(16) 29622(6) α [deg] 90 90 90 β [deg] 99535(7) 90 101410(9) γ [deg] 90 90 90
V [Aring3] 25225(3) 32558(5) 10060(1) Z 2 4 8
ρ(calc) [Mg mndash3] 1607 1848 1430 micro [mmndash1] 0163 3558 0807
Absorption Correction 035396 065857 Tmin Tmax 10000 10000
F(000) 1232 1776 4400 ndash17 le H le 17 ndash14 le H le 14 ndash27 le H le 27
Index Ranges ndash14 le K le 13 ndash14 le K le 14 ndash15 le K le 15 ndash17 le L le 17 ndash33 le L le 33 ndash32 le L le 32
2θrange [deg] 275 to 2503 302 to 2751 143 to 2309 Temperature [K] 140 100 150
Reflections Collected 15376 125178 58750 Reflections Unique 4371 3741 14111
Parameters 379 210 1171 GOOF 1053 1213 0946
Final R wR2 (2σ) 0075 01551 00290 00533 00610 01180 Final R wR2 (all) 01535 01994 00352 00559 01259 01387
Large Res Peak [e Aringndash3] 0387 0365 0563
141
Table L-3
Compound PhndashFrarrAl(ORF)3 Me3SindashFndashAl(ORF)3 [Ag(tol)3]+[FAl(ORF)3]ndash
RF = helliphellip C(CF3)3 (D-1) C(CF3)3 (E-1) C(CF3)3 (E-2) CCDC-Number 662085 671129 671130
Empirical Formula AlC18F28H5O3 C15H9AlF28O3Si C33H24AgAlF28O3 Crystal Size [mm3] 027 x 011 x 008 04 x 03 x 02 024 x 021 x 017
Crystal System Monoclinic Orthorombic Monoclinic Space Group P21n P21212 P21c
a [Aring] 106289(4) 10037(2) 206944(19) b [Aring] 213339(8) 13519(3) 16945(2) c [Aring] 118219(5) 20367(4) 23785(3) α [deg] 90 90 90 β [deg] 96733(2) 90 103244(8) γ [deg] 90 90 90
V [Aring3] 266220(18) 27636(10) 81096(15) Z 4 4 8
ρ(calc) [Mg mndash3] 2066 1981 1860 micro [mmndash1] 0297 0327 0683
Absorption Correction 09240 08513 07951 Tmin Tmax 09766 09423 08917
F(000) 1608 1608 4464 ndash13 le H le 13 ndash13 le H le 13 ndash26 le H le 26
Index Ranges ndash26 le K le 25 ndash17 le K le 17 ndash22 le K le 22 ndash14 le L le 14 ndash26 le L le 26 ndash30 le L le 30
2θrange [deg] 191 to 2661 336 to 2752 336 to 2748 Temperature [K] 173 100 100
Reflections Collected 72201 49815 210376 Reflections Unique 5486 6282 18530
Parameters 471 434 1250 GOOF 1064 1058 1174
Final R wR2 (2σ) 00445 00844 00295 00655 00511 00682 Final R wR2 (all) 00735 01016 00382 00716 00969 00809
Large Res Peak [e Aringndash3] 0671 0377 0625
142
Table L-4
Compound [Ag(12-F2Ph)3]+ [Ph3C]+[FAl(ORF)3]ndash [N(Bu)4]+
[(ORF)3AlndashFndash
Al(ORF)3]ndash [(RFO)3AlndashFndashAl(ORF)2ndash
Al(ORF)3]ndash
RF = helliphellip C(CF3)3 (E-5) C(CF3)3 (E-4) C(CF3)3 (E-6) CCDC-Number 671162 671131 671673
Empirical Formula C168H48Ag4Al8F244O24 C31H15AlF28O3 C48H36Al3F74NO8 Crystal Size [mm3] 02 x 02 x 02 021 x 017 x 014 05 x 02 x 02
Crystal System Triclinic Monoclinic Triclinic Space Group Pndash1 P21n P21m
a [Aring] 15562(3) 104637(10) 11122(2) b [Aring] 17773(2) 172641(14) 17431(4) c [Aring] 22668(3) 20736(3) 20190(4) α [deg] 76166(9) 90 90 β [deg] 83981(10) 98664(11) 10368(3) γ [deg] 81674(11) 90 90
V [Aring3] 60074(16) 37031(7) 38033(13) Z 1 4 2
ρ(calc) [Mg mndash3] 2138 1784 1958 micro [mmndash1] 0602 0231 0281
Absorption Correction semi empirical 0631 none Tmin Tmax 0940 0970 none
F(000) 3736 1960 2200 ndash20 le H le 20 ndash8 le H le 12 ndash13 le H le 13
Index Ranges ndash23 le K le 23 ndash20 le K le 15 ndash18 le K le 20 ndash29 le L le 29 ndash24 le L le 24 ndash23 le L le 23
2θrange [deg] 119 to 2750 256 to 2503 156 to 2468 Temperature [K] 100 100 150
Reflections Collected 99039 19570 34237 Reflections Unique 26375 6361 12803
Parameters 2167 568 1237 GOOF 1079 1063 1051
Final R wR2 (2σ) 00735 01285 00705 01364 00614 01577 Final R wR2 (all) 01533 01662 01230 01650 00923 01878
Large Res Peak [e Aringndash3] 1383 1343 0686
143
M Atomic Coordinates Table M-1 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1A) 5453(5) 205(2) 4279(3) 113(2) F(2A) 5969(4) 785(2) 3931(3) 102(2) F(3A) 5157(4) 338(1) 3161(3) 94(2) F(4A) 2963(5) 166(1) 4485(2) 105(2) F(5A) 2876(5) 42(1) 3383(3) 99(2) F(6A) 1670(4) 494(1) 3698(2) 83(1) F(7A) 3046(4) 404(1) 1531(3) 95(2) F(8A) 1708(4) 33(1) 1920(3) 85(1) F(9A) 1579(5) 101(1) 788(3) 102(2) F(10A) ndash821(4) 258(1) 1043(3) 87(1) F(11A) ndash380(4) 429(1) 2149(2) 79(1) F(12A) ndash1098(3) 865(1) 1361(2) 83(1) F(13A) 3726(5) 1244(2) 791(3) 106(2) F(14A) 3207(4) 1841(2) 813(2) 110(2) F(15A) 5065(4) 1699(2) 690(2) 101(2) F(16A) 6595(4) 1365(2) 1725(3) 130(2) F(17A) 6114(4) 1381(2) 2761(3) 141(3) F(18A) 5278(4) 941(2) 2010(3) 111(2) F(19A) 363(5) 1806(2) 4521(2) 100(2) F(20A) 1277(5) 1271(2) 4300(3) 109(2) F(21A) 2286(5) 1815(2) 4392(2) 107(2) F(22A) ndash501(4) 1162(1) 3042(3) 92(1) F(23A) ndash1413(4) 1675(2) 3395(3) 99(2) F(24A) ndash891(4) 1673(2) 2367(3) 100(2) O(1A) 3405(3) 911(1) 3246(2) 44(1) O(2A) 1534(3) 927(1) 1944(2) 40(1) O(3A) 3574(3) 1494(1) 2165(2) 38(1) O(4A) 1635(3) 1556(1) 2985(2) 38(1) O(5A) 742(4) 1881(1) 1236(2) 55(1) O(6A) 4606(4) 1863(1) 3795(3) 70(1) C(1A) 3828(5) 668(2) 3825(3) 52(2) C(2A) 5096(7) 491(2) 3785(5) 76(2) C(3A) 2868(7) 336(2) 3851(4) 68(2) C(4A) 1002(5) 665(2) 1405(3) 46(1) C(5A) 1794(7) 297(2) 1406(4) 68(2) C(6A) ndash317(6) 548(2) 1501(4) 57(2) C(7A) 4545(5) 1605(2) 1829(3) 45(1) C(8A) 4149(7) 1592(3) 1040(4) 68(2) C(9A) 5637(6) 1331(3) 2080(5) 82(2) C(10A) 778(5) 1728(2) 3345(3) 45(1) C(11A) 1141(7) 1657(3) 4132(4) 73(2) C(12A) ndash526(6) 1565(2) 3042(5) 67(2) C(13A) 162(7) 1712(2) 554(4) 75(2) C(14A) ndash1269(8) 1743(3) 378(5) 101(3) C(15A) 801(9) 2308(2) 1213(6) 117(4) C(16A) 1506(10) 2482(3) 1747(7) 159(6) C(17A) 4674(10) 2263(3) 3584(8) 150(5) C(18A) 3868(12) 2531(3) 3654(9) 177(7) C(19A) 5145(9) 1743(3) 4546(5) 108(3) C(20A) 6524(9) 1747(3) 4703(5) 124(4) Li(1A) 1587(8) 974(3) 2934(5) 43(2) Li(2A) 1723(8) 1527(3) 1958(5) 38(2) Li(3A) 3482(8) 1502(3) 3187(5) 42(2)
144
Li(4A) 3349(8) 920(3) 2236(5) 46(2) F(1B) 6235(3) 1631(1) 8898(3) 86(1) F(2B) 5904(4) 2221(1) 9255(3) 102(2) F(3B) 5490(4) 2083(2) 8132(3) 93(1) F(4B) 2052(4) 2043(1) 8762(2) 80(1) F(5B) 3326(5) 2440(1) 8367(2) 91(1) F(6B) 3506(5) 2358(1) 9496(2) 94(2) F(7B) 1977(6) 2417(2) 5829(3) 133(2) F(8B) 3340(4) 2112(2) 6635(3) 119(2) F(9B) 1973(5) 2498(1) 6949(3) 114(2) F(10B) ndash474(5) 2275(1) 5976(3) 115(2) F(11B) ndash206(4) 2116(2) 7086(3) 100(2) F(12B) ndash833(4) 1677(1) 6286(3) 101(2) F(13B) 3013(5) 814(3) 5736(3) 176(3) F(14B) 4016(7) 1344(2) 5947(4) 175(3) F(15B) 4945(5) 831(2) 5636(2) 122(2) F(16B) 6060(4) 800(3) 7792(3) 170(3) F(17B) 6629(4) 839(2) 6767(3) 153(3) F(18B) 5835(5) 1340(2) 7232(4) 146(2) F(19B) ndash876(4) 1030(2) 7405(3) 124(2) F(20B) ndash1378(4) 997(2) 8446(3) 120(2) F(21B) ndash171(4) 1468(2) 8195(3) 98(2) F(22B) 1536(4) 1204(1) 9384(2) 85(1) F(23B) 255(4) 733(2) 9502(2) 92(2) F(24B) 2108(4) 599(1) 9349(2) 87(1) O(1B) 3619(3) 1562(1) 8288(2) 39(1) O(2B) 1730(3) 1608(1) 6984(2) 42(1) O(3B) 3598(3) 986(1) 7180(2) 39(1) O(4B) 1668(3) 970(1) 8000(2) 35(1) O(5B) 694(4) 661(1) 6315(2) 53(1) O(6B) 4509(4) 598(1) 8889(2) 56(1) C(1B) 4115(5) 1810(2) 8836(3) 46(1) C(2B) 5453(6) 1942(2) 8786(4) 66(2) C(3B) 3279(7) 2172(2) 8873(4) 65(2) C(4B) 1282(6) 1865(2) 6434(4) 58(2) C(5B) 2130(8) 2218(3) 6448(5) 88(2) C(6B) ndash71(7) 1987(2) 6445(5) 76(2) C(7B) 4440(5) 834(2) 6795(3) 51(1) C(8B) 4140(7) 950(3) 6031(4) 87(2) C(9B) 5720(7) 950(3) 7113(5) 92(3) C(10B) 740(5) 827(2) 8341(3) 43(1) C(11B) ndash443(6) 1070(3) 8090(4) 76(2) C(12B) 1139(6) 842(2) 9136(3) 55(2) C(13B) 550(7) 264(2) 6528(5) 81(2) C(14B) 1281(10) -36(3) 6237(6) 112(3) C(15B) 119(7) 775(2) 5578(4) 73(2) C(16B) ndash1269(8) 767(3) 5441(5) 99(3) C(17B) 4418(8) 172(2) 8866(5) 89(3) C(18B) 3595(7) 38(2) 8210(4) 75(2) C(19B) 5146(7) 746(2) 9584(4) 68(2) C(20B) 6561(7) 686(3) 9712(4) 92(3) Li(1B) 1787(8) 1561(3) 7978(5) 43(2) Li(2B) 1741(8) 1007(3) 6980(5) 40(2) Li(3B) 3514(8) 963(3) 8193(5) 37(2) Li(4B) 3568(9) 1570(3) 7282(5) 49(2)
145
Table M-2 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) F(1) 793(3) 2211(2) 1634(2) 69(1) F(2) 2837(3) 1764(2) 1846(3) 83(1) F(3) 1536(5) 2007(2) 2948(2) 95(1) F(4) 690(5) 950(2) 551(2) 96(1) F(5) 2507(4) 337(3) 1020(3) 105(1) F(6) 535(4) -209(2) 1121(2) 93(1) F(7) 1101(5) ndash1132(2) 2548(3) 106(1) F(8) 2781(4) ndash1100(2) 3443(4) 112(2) F(9) 755(5) ndash1264(2) 3962(3) 111(2) F(10) 1460(5) 1079(2) 4430(2) 90(1) F(11) 3269(3) 339(3) 4291(2) 91(1) F(12) 1511(3) -66(2) 5006(2) 80(1) O(1) -337(3) 839(2) 2357(2) 50(1) O(2) 1916(3) 410(2) 2708(2) 41(1) O(3) ndash3030(3) 1253(2) 1126(2) 59(1) O(4) ndash2940(3) 1713(2) 3105(2) 44(1) O(5) ndash3082(3) -61(2) 2517(2) 58(1) C(1) 930(4) 866(3) 2120(3) 39(1) C(2) 1284(5) 22(3) 3434(3) 47(1) C(3) 1548(5) 1719(3) 2140(3) 51(1) C(4) 1171(6) 489(3) 1189(3) 61(1) C(5) 1509(6) ndash870(3) 3335(5) 72(2) C(6) 1901(5) 342(3) 4282(3) 57(1) C(7) ndash2563(10) 1810(6) 522(6) 140(4) C(8) ndash3487(11) 1883(6) ndash178(7) 161(5) C(9) ndash4561(9) 1363(6) ndash50(6) 119(3) C(10) ndash4113(7) 832(4) 688(4) 87(2) C(11) ndash4381(5) 1965(4) 3125(4) 68(2) C(12) ndash4629(8) 2283(6) 4039(6) 118(3) C(13) ndash3421(13) 2151(8) 4503(5) 183(6) C(14) ndash2259(6) 1901(4) 3926(3) 68(2) C(15) ndash4021(6) ndash216(3) 3211(4) 74(2) C(16) ndash3853(8) ndash1106(3) 3418(4) 81(2) C(17) ndash3273(14) ndash1414(5) 2689(8) 190(7) C(18) ndash2613(6) ndash811(3) 2143(4) 67(2) Li(1) ndash2187(7) 961(4) 2250(4) 39(1)
146
Table M-3 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-5 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 59(8) 2840(6) 3239(3) 39(2) Li(2) ndash1873(8) 2187(6) 2549(3) 41(2) F(1) 2209(3) 1890(2) 3748(1) 36(1) F(2) 2646(3) 1555(2) 3040(1) 37(1) F(3) 4012(3) 2003(2) 3488(1) 39(1) F(4) 3680(3) 2826(2) 2539(1) 45(1) F(5) 4538(2) 3520(2) 3101(1) 43(1) F(6) 3203(3) 4143(2) 2690(1) 50(1) F(7) 89(3) 741(2) 3229(1) 44(1) F(8) ndash1336(3) 887(2) 2734(1) 45(1) F(9) ndash1555(3) 41(2) 3314(1) 48(1) F(10) ndash3467(3) 1303(2) 3130(1) 50(1) F(11) ndash3191(3) 876(2) 3839(1) 55(1) F(12) ndash3436(3) 2217(2) 3690(1) 45(1) O(1) 1493(3) 2909(2) 2952(1) 27(1) O(2) ndash1364(3) 2285(2) 3156(1) 27(1) C(1) 2494(4) 3058(3) 3214(1) 26(1) C(2) 2876(4) 2138(3) 3386(2) 29(1) C(3) 3499(4) 3400(3) 2891(2) 32(1) C(4) 2271(4) 3750(3) 3608(1) 25(1) C(5) 2869(4) 3767(3) 4047(2) 27(1) C(6) 2536(5) 4377(3) 4382(2) 34(1) C(7) 1648(5) 4975(3) 4309(2) 34(1) C(8) 1114(4) 4981(3) 3878(2) 33(1) C(9) 1403(4) 4396(3) 3522(2) 29(1) C(10) 3905(5) 3205(4) 4190(2) 38(1) C(11) 1325(6) 5619(4) 4685(2) 50(2) C(12) 754(5) 4576(3) 3063(2) 35(1) C(13) ndash1558(4) 1623(3) 3463(2) 28(1) C(14) ndash1091(5) 801(3) 3200(2) 35(1) C(15) ndash2920(5) 1507(3) 3534(2) 35(1) C(16) ndash937(4) 1809(3) 3944(1) 24(1) C(17) ndash422(5) 1173(3) 4238(2) 33(1) C(18) 322(4) 1442(3) 4603(2) 33(1) C(19) 552(4) 2294(3) 4706(1) 32(1) C(20) ndash58(4) 2904(3) 4449(2) 31(1) C(21) ndash831(4) 2688(3) 4078(1) 28(1) C(22) ndash615(6) 217(3) 4204(2) 44(1) C(23) 1397(5) 2555(4) 5091(2) 44(1) C(24) ndash1521(5) 3459(3) 3890(2) 34(1) ________________________________________________________________________________
147
Table M-4 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-6 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Li(1) 912(6) ndash187(7) 444(6) 27(2) Li(2) ndash518(6) ndash994(7) 1102(6) 31(2) Li(3) 121(6) 1818(7) 349(6) 27(2) F(1) 1124(2) ndash4394(2) 1951(2) 38(1) F(2) 53(2) ndash3986(3) 817(2) 42(1) F(3) 91(2) ndash3175(2) 2137(2) 43(1) F(4) 1795(2) ndash4077(2) 311(2) 34(1) F(5) 898(2) ndash2873(2) ndash440(2) 33(1) F(6) 2260(2) ndash2366(2) 151(2) 33(1) F(7) 1866(2) 1411(3) 2037(2) 35(1) F(8) 2366(2) 3099(3) 1848(2) 42(1) F(9) 991(2) 2664(2) 1280(2) 36(1) F(10) 3198(2) 3305(3) 339(2) 46(1) F(11) 1763(2) 3679(3) ndash61(2) 47(1) F(12) 2446(2) 2628(3) ndash926(2) 46(1) F(13) ndash205(2) 440(2) 781(2) 23(1) O(1) 610(2) ndash1683(3) 908(2) 24(1) O(2) 1320(2) 1318(3) 48(2) 21(1) C(1) 1199(3) ndash2570(4) 1220(4) 23(1) C(2) 617(4) ndash3532(4) 1545(4) 30(1) C(3) 1555(4) ndash2987(4) 324(4) 24(1) C(4) 1979(3) ndash2195(4) 2028(3) 23(1) C(5) 2863(4) ndash2679(4) 2199(4) 25(1) C(6) 3544(4) ndash2188(4) 2855(4) 28(1) C(7) 3403(4) ndash1238(5) 3374(4) 32(1) C(8) 2501(4) ndash831(4) 3247(4) 29(1) C(9) 1794(3) ndash1301(4) 2608(4) 23(1) C(10) 3183(4) ndash3752(5) 1774(4) 38(2) C(11) 4159(4) ndash690(5) 4057(5) 51(2) C(12) 857(4) ndash783(4) 2669(4) 29(1) C(13) 2120(3) 1798(4) 490(4) 22(1) C(14) 1869(4) 2242(4) 1436(4) 31(1) C(15) 2389(4) 2857(4) ndash33(4) 31(1) C(16) 2948(3) 941(4) 591(3) 19(1) C(17) 3682(4) 888(4) 1355(4) 28(1) C(18) 4345(4) 42(5) 1381(4) 31(1) C(19) 4341(4) ndash763(4) 694(4) 30(1) C(20) 3655(3) ndash651(4) ndash69(4) 26(1) C(21) 2971(3) 163(4) ndash142(4) 24(1) C(22) 3875(4) 1719(5) 2161(4) 37(2) C(23) 5053(4) ndash1669(5) 762(4) 40(2) C(24) 2308(4) 111(5) ndash1060(4) 31(1)
148
Table M-5 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for B-7 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Br(1) 363(1) 190(1) ndash710(1) 36(1) Ga(1) 1141(1) 1141(1) 0 22(1) Cl(1) 3522(1) 5081(1) 416(1) 37(1) F(1) 1022(2) 4826(2) 645(1) 30(1) F(2) 128(2) 3143(2) 755(1) 36(1) F(3) ndash901(2) 4676(2) 543(1) 35(1) F(4) ndash634(1) 2953(2) ndash835(1) 27(1) F(5) ndash1315(2) 2498(2) ndash89(1) 36(1) F(6) ndash1578(2) 4277(2) ndash397(1) 33(1) O(1) 1223(2) 2818(2) ndash72(1) 18(1) C(1) 407(2) 3774(2) ndash115(1) 19(1) C(2) 986(2) 4769(2) ndash458(1) 16(1) C(3) 759(2) 6017(3) ndash404(1) 20(1) C(4) 1379(3) 6822(2) ndash716(1) 25(1) C(5) 2198(3) 6479(3) ndash1080(1) 26(1) C(6) 2374(2) 5263(3) ndash1146(1) 23(1) C(7) 1775(2) 4391(2) ndash857(1) 18(1) C(8) 147(3) 4128(3) 460(1) 26(1) C(9) ndash792(2) 3370(3) ndash362(1) 25(1) C(10) ndash134(3) 6610(3) ndash47(1) 29(1) C(11) 2856(3) 7381(3) ndash1415(1) 41(1) C(12) 2018(2) 3118(2) ndash1045(1) 22(1) C(13) 5066(3) 5328(3) 278(1) 41(1) Li(1) 2991(4) 2991(4) 0 25(1)
149
Table M-6 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for C-1 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Li(1) 2423(4) 5312(7) 2366(3) 42(2) Li(2) 2556(4) 10326(8) 2550(3) 43(2) SiA 2908(7) 4151(13) 610(5) 3(6) Si(1) 522(1) 3688(1) 2963(1) 46(1) Si(2) 1164(1) 7494(1) 1146(1) 40(1) Si(3) 796(1) 1673(1) 434(1) 40(1) Si(4) 3128(1) 3487(2) 792(1) 53(1) Si(5) 1697(1) 9179(2) 4162(1) 66(1) Si(6) 4744(1) 8726(2) 2421(1) 58(1) Si(7) 4571(1) 6464(1) 4126(1) 46(1) Si(8) 3937(1) 12575(1) 3919(1) 47(1) Al(1) 1661(1) 4140(1) 1725(1) 29(1) Al(2) 3246(1) 9252(1) 3272(1) 30(1) F(1) 2101(1) 3332(3) 2985(1) 51(1) F(2) 2455(1) 4725(2) 3064(1) 42(1) F(3) 1933(1) 4292(3) 3486(1) 55(1) F(4) 1745(1) 6221(2) 2759(1) 46(1) F(5) 1238(1) 5694(3) 3183(1) 52(1) F(6) 886(1) 5899(2) 2438(1) 46(1) F(7) 253(1) 5313(3) 1512(1) 55(1) F(8) -13(1) 6070(3) 860(1) 55(1) F(9) 2(1) 4552(3) 861(1) 53(1) F(10) 696(1) 4508(3) 318(1) 53(1) F(11) 631(1) 6022(3) 285(1) 54(1) F(12) 1435(1) 5356(3) 528(1) 52(1) F(13) 1079(1) 1674(2) 2105(1) 43(1) F(14) 566(1) 2564(2) 1560(1) 44(1) F(15) 681(1) 1093(2) 1421(1) 46(1) F(16) 1693(1) 526(2) 1417(1) 49(1) F(17) 2308(1) 1584(2) 1419(1) 45(1) F(18) 2109(1) 1252(2) 2058(1) 43(1) F(19) 3037(1) 3209(3) 2034(1) 49(1) F(20) 3691(1) 4002(3) 1877(1) 55(1) F(21) 3281(1) 4554(2) 2372(1) 47(1) F(23) 2584(1) 5996(2) 1122(1) 51(1) F(24) 3443(1) 5644(3) 1427(1) 57(1) F(25) 2950(1) 6142(2) 1863(1) 47(1) F(101) 1647(2) 9705(3) 2511(1) 65(1) F(102) 1776(2) 8417(3) 2912(1) 62(1) F(103) 1161(1) 9420(3) 2994(2) 87(1) F(104) 2042(2) 11341(2) 2962(1) 55(1) F(105) 2333(2) 11294(3) 3715(1) 63(1) F(106) 1469(2) 11060(3) 3359(1) 73(1) F(107) 3138(1) 7520(2) 4148(1) 45(1) F(108) 2536(1) 6905(2) 3557(1) 46(1) F(109) 3196(1) 6048(3) 3974(1) 52(1) F(110) 2880(1) 6409(2) 2788(1) 37(1) F(111) 3550(1) 5614(2) 3250(1) 43(1) F(112) 3731(1) 6719(2) 2819(1) 43(1) F(113) 3334(1) 11175(2) 2169(1) 46(1) F(114) 4144(1) 11004(2) 2658(1) 47(1) F(115) 4000(1) 10580(2) 1933(1) 48(1) F(116) 3105(1) 8241(2) 2108(1) 45(1)
150
F(117) 3420(1) 9049(3) 1629(1) 57(1) F(118) 2734(1) 9577(2) 1855(1) 49(1) F(119) 4058(2) 9574(3) 4721(1) 83(1) F(120) 4193(2) 11069(3) 4766(1) 65(1) F(121) 3377(2) 10519(3) 4444(1) 70(1) F(122) 4819(2) 9405(3) 4236(2) 92(2) F(123) 4742(1) 10277(3) 3637(1) 75(1) F(124) 4966(1) 10877(3) 4323(1) 62(1) O(1) 2593(1) 9803(3) 3166(1) 35(1) O(2) 1115(1) 4487(3) 1261(1) 34(1) O(3) 1694(1) 2927(3) 1745(1) 31(1) O(4) 3750(2) 9576(3) 3771(1) 40(1) O(11) 1698(1) 4679(3) 2269(1) 35(1) O(12) 3209(1) 8042(3) 3242(1) 34(1) O(13) 3295(1) 9767(3) 2740(1) 32(1) O(14) 2302(1) 4691(3) 1747(1) 33(1) C(1) 1491(2) 4595(4) 2660(2) 34(1) C(2) 1991(2) 4231(5) 3055(2) 39(2) C(3) 1339(2) 5594(5) 2764(2) 40(2) C(4) 992(2) 3920(4) 2573(2) 38(1) C(5) 96(3) 2668(6) 2668(2) 71(2) C(6) 913(3) 3337(6) 3572(2) 70(2) C(7) 59(2) 4708(6) 2966(3) 71(2) C(8) 880(2) 5334(4) 1055(2) 32(1) C(9) 274(2) 5318(4) 1067(2) 38(1) C(10) 906(2) 5304(5) 544(2) 41(2) C(11) 1193(2) 6201(4) 1309(2) 36(1) C(12) 1631(3) 8027(5) 1691(3) 75(2) C(13) 1457(3) 7738(5) 646(2) 64(2) C(14) 468(2) 8025(5) 1042(2) 52(2) C(15) 1439(2) 2158(4) 1473(2) 31(1) C(16) 1263(2) 2367(4) 938(2) 35(1) C(17) 937(2) 1863(4) 1641(2) 35(1) C(18) 1883(2) 1367(4) 1586(2) 36(1) C(19) 56(2) 1943(5) 394(2) 57(2) C(20) 915(3) 376(5) 441(2) 64(2) C(21) 978(2) 2178(5) ndash86(2) 48(2) C(22) 2757(2) 4574(4) 1565(2) 35(1) C(23) 2622(2) 3993(4) 1113(2) 36(1) C(24) 2937(2) 5575(4) 1492(2) 39(1) C(25) 3194(2) 4074(5) 1958(2) 41(2) C(26) 3683(3) 4272(6) 744(2) 64(2) C(27) 3447(3) 2374(5) 1079(2) 58(2) C(27A) 2870(30) 5260(50) 350(20) 17(17) C(28) 2648(3) 3201(6) 208(2) 69(2) C(102) 1670(2) 9325(5) 2935(2) 52(2) C(103) 1985(3) 10875(5) 3343(2) 48(2) C(104) 2202(2) 9331(5) 3798(2) 46(2) C(105) 2181(4) 8765(8) 4740(3) 114(4) C(106) 1167(5) 8308(7) 3898(4) 134(4) C(107) 1372(3) 10268(6) 4283(2) 69(2) C(108) 3437(2) 7226(4) 3475(2) 32(1) C(109) 3079(2) 6908(4) 3792(2) 35(1) C(110) 3405(2) 6486(4) 3092(2) 37(1) C(111) 4050(2) 7342(4) 3770(2) 35(1) C(112) 5177(2) 7210(5) 4407(2) 55(2) C(113) 4814(3) 5614(5) 3738(3) 74(2) C(114) 4346(3) 5832(6) 4577(3) 80(2) C(115) 3619(2) 9599(4) 2430(2) 33(1) C(116) 4128(2) 8996(4) 2648(2) 33(1) C(117) 3777(2) 10587(4) 2296(2) 37(1) C(118) 3227(2) 9115(5) 2000(2) 38(1)
151
C(119) 5126(2) 7835(5) 2856(2) 59(2) C(120) 5191(3) 9823(7) 2474(4) 116(4) C(121) 4562(4) 8240(11) 1825(3) 175(7) C(122) 4018(2) 10379(4) 4000(2) 38(1) C(123) 3807(2) 11294(4) 3735(2) 37(1) C(124) 4632(3) 10239(5) 4053(2) 50(2) C(125) 3921(3) 10376(5) 4489(2) 57(2) C(126) 4674(3) 12905(5) 4198(2) 65(2) C(127) 3683(3) 13183(5) 3341(2) 71(2) C(128) 3509(3) 12942(5) 4307(3) 74(2) C(301) 2630(30) 5720(50) 5250(20) 340(30) C(302) 2791(12) 5270(30) 5049(10) 149(9) C(303) 3149(10) 6070(20) 5301(8) 131(8) C(304) 3267(14) 6820(30) 5519(11) 209(14) C(305) 3642(11) 7560(20) 5507(9) 171(10) C(306) 2033(10) 5360(20) 4716(8) 264(10) C(311) 1265(11) 5670(20) 4371(9) 132(10) C(313) 2304(19) 4610(40) 4711(16) 206(17) C(314) 2600(15) 4620(30) 5148(13) 162(12) C(315) 3180(20) 5030(30) 5432(16) 206(16) C(316) 3718(9) 5222(17) 5572(7) 100(7) C(404) 2118(2) 9816(4) 3324(2) 38(1)
152
Table M-7 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for D-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1775(1) 738(1) 2130(1) 20(1) O(1) 1847(2) 1061(1) 818(2) 24(1) O(2) 1879(2) 1276(1) 3191(2) 25(1) O(3) 2418(2) 32(1) 2477(2) 25(1) F(1) 46(2) 564(1) 1892(1) 27(1) C(1) ndash1018(3) 919(1) 2209(2) 23(1) C(2) ndash1081(3) 1537(1) 1920(3) 28(1) C(3) ndash2102(3) 1866(2) 2257(3) 33(1) C(4) ndash2980(3) 1565(2) 2836(3) 36(1) C(5) ndash2863(3) 933(2) 3088(3) 35(1) C(6) ndash1850(3) 591(1) 2771(3) 29(1) C(7) 2679(3) 1407(1) 276(2) 25(1) C(8) 4041(3) 1152(2) 570(3) 36(1) C(9) 2628(3) 2104(2) 653(3) 36(1) C(10) 2283(3) 1355(2) ndash1021(3) 34(1) C(11) 2090(3) 1420(1) 4322(2) 25(1) C(12) 1023(3) 1878(2) 4595(3) 36(1) C(13) 3404(3) 1734(1) 4576(3) 32(1) C(14) 2034(3) 819(2) 5055(2) 32(1) C(15) 2500(3) ndash599(1) 2315(2) 26(1) C(16) 1602(3) ndash937(1) 3064(3) 36(1) C(17) 2119(3) ndash767(1) 1043(3) 34(1) C(18) 3889(3) ndash800(2) 2680(3) 40(1) F(2) 4225(2) 1017(1) 1690(2) 44(1) F(3) 4931(2) 1558(1) 353(2) 50(1) F(4) 4220(2) 625(1) 18(2) 47(1) F(5) 3135(2) 2490(1) ndash56(2) 45(1) F(6) 3253(2) 2176(1) 1687(2) 53(1) F(7) 1438(2) 2283(1) 699(2) 53(1) F(8) 2006(2) 765(1) ndash1315(2) 45(1) F(9) 3198(2) 1550(1) ndash1622(2) 46(1) F(10) 1255(2) 1697(1) ndash1336(2) 47(1) F(11) 1317(2) 2159(1) 5604(2) 51(1) F(12) ndash61(2) 1570(1) 4630(2) 43(1) F(13) 839(2) 2319(1) 3804(2) 46(1) F(14) 3784(2) 1765(1) 5694(2) 41(1) F(15) 4274(2) 1413(1) 4098(2) 41(1) F(16) 3380(2) 2316(1) 4165(2) 45(1) F(17) 3087(2) 482(1) 5048(2) 40(1) F(18) 1061(2) 460(1) 4650(2) 41(1) F(19) 1906(2) 951(1) 6140(2) 49(1) F(20) 1953(2) ndash841(1) 4149(2) 67(1) F(21) 448(2) ndash711(1) 2857(2) 66(1) F(22) 1529(3) ndash1541(1) 2882(2) 91(1) F(23) 2811(3) ndash469(1) 379(2) 69(1) F(24) 2220(3) ndash1361(1) 829(2) 86(1) F(25) 952(2) ndash602(2) 723(2) 97(1) F(26) 4041(3) ndash1405(1) 2614(3) 113(1) F(27) 4258(2) ndash635(1) 3730(2) 73(1) F(28) 4664(2) ndash531(2) 2060(2) 91(1)
153
Table M-8 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-1 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 2980(1) 4868(1) 1724(1) 18(1) Si(1) 6261(1) 4701(1) 1333(1) 20(1) F(1) 4577(1) 5019(1) 1332(1) 31(1) F(2) 4493(1) 6057(1) 3452(1) 35(1) F(3) 5282(1) 4595(1) 3604(1) 36(1) F(4) 3745(2) 5158(1) 4248(1) 39(1) F(5) 4041(1) 3119(1) 2940(1) 34(1) F(6) 3061(2) 3288(1) 3876(1) 36(1) F(7) 1901(1) 3198(1) 2985(1) 34(1) F(8) 1826(1) 6147(1) 3400(1) 39(1) F(9) 1143(1) 4780(1) 3837(1) 40(1) F(10) 899(1) 5039(1) 2793(1) 39(1) F(11) 2882(1) 1796(1) 1693(1) 37(1) F(12) 823(1) 2026(1) 1932(1) 36(1) F(13) 1345(2) 1348(1) 1009(1) 43(1) F(14) ndash157(1) 3852(1) 1579(1) 42(1) F(15) ndash502(1) 2799(1) 804(1) 41(1) F(16) 328(2) 4233(1) 583(1) 43(1) F(17) 1736(2) 2662(1) ndash21(1) 44(1) F(18) 2931(2) 3917(1) 268(1) 42(1) F(19) 3582(1) 2440(1) 505(1) 43(1) F(20) ndash408(1) 6456(1) 1233(1) 38(1) F(21) 443(1) 6394(1) 264(1) 39(1) F(22) 203(1) 7804(1) 753(1) 41(1) F(23) 3122(1) 6127(1) 220(1) 36(1) F(24) 2715(1) 7698(1) 239(1) 40(1) F(25) 4204(1) 7068(1) 883(1) 37(1) F(26) 2347(2) 8390(1) 1512(1) 44(1) F(27) 3171(2) 7192(1) 2089(1) 43(1) F(28) 1060(2) 7485(1) 2114(1) 44(1) O(1) 3481(1) 4938(1) 2525(1) 23(1) O(2) 2464(1) 3697(1) 1542(1) 23(1) O(3) 2023(1) 5775(1) 1382(1) 22(1) C(1) 6772(3) 5066(2) 502(1) 41(1) C(2) 6955(2) 5442(2) 2003(1) 39(1) C(3) 6213(2) 3365(2) 1496(1) 30(1) C(4) 3103(2) 4706(2) 3153(1) 21(1) C(5) 4175(2) 5144(2) 3626(1) 26(1) C(6) 3027(2) 3560(2) 3245(1) 27(1) C(7) 1717(2) 5175(2) 3308(1) 28(1) C(8) 1775(2) 3094(2) 1127(1) 22(1) C(9) 1705(2) 2046(2) 1443(1) 28(1) C(10) 337(2) 3494(2) 1016(1) 30(1) C(11) 2511(2) 3023(2) 454(1) 30(1) C(12) 1931(2) 6723(2) 1153(1) 21(1) C(13) 512(2) 6854(2) 842(1) 28(1) C(14) 3005(2) 6911(2) 609(1) 28(1) C(15) 2124(2) 7469(2) 1722(1) 32(1)
154
Table M-9 Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Aring2
x 103) for E-2 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) 1052(1) 7454(1) 2941(1) 15(1) F(1) 1011(1) 7762(1) 2261(1) 23(1) F(2) ndash146(1) 8593(1) 2592(1) 32(1) F(3) ndash799(1) 7718(1) 2107(1) 39(1) F(4) ndash1130(1) 8438(1) 2741(1) 40(1) F(5) ndash730(1) 6262(1) 2580(1) 40(1) F(6) ndash1429(1) 6913(1) 2945(1) 45(1) F(7) ndash646(1) 6240(1) 3500(1) 39(1) F(8) ndash848(1) 7828(1) 3864(1) 39(1) F(9) ndash29(1) 8537(1) 3734(1) 34(1) F(10) 157(1) 7387(1) 4114(1) 38(1) F(11) 1758(1) 9309(1) 2606(1) 35(1) F(12) 945(1) 9613(1) 2989(1) 43(1) F(13) 1904(1) 10163(1) 3299(1) 42(1) F(14) 1234(1) 9543(1) 4154(1) 44(1) F(15) 2309(1) 9546(2) 4407(1) 45(1) F(16) 1756(1) 8502(1) 4527(1) 41(1) F(17) 2756(1) 8080(1) 4022(1) 35(1) F(18) 2932(1) 9109(1) 3540(1) 36(1) F(19) 2498(1) 8059(1) 3089(1) 32(1) F(20) 865(1) 5769(1) 3851(1) 36(1) F(21) 1590(1) 6665(1) 4170(1) 38(1) F(22) 1850(1) 5433(1) 4311(1) 38(1) F(23) 2782(1) 6391(1) 3888(1) 38(1) F(24) 2724(1) 5159(1) 3636(1) 35(1) F(25) 2723(1) 6070(1) 3000(1) 37(1) F(26) 1477(1) 4555(1) 3286(1) 34(1) F(27) 1709(1) 5105(1) 2534(1) 34(1) F(28) 772(1) 5337(1) 2749(1) 35(1) O(1) 282(1) 7168(1) 3039(1) 21(1) O(2) 1351(1) 8203(1) 3429(1) 20(1) O(3) 1545(1) 6617(1) 3030(1) 20(1) C(1) ndash320(2) 7428(2) 3096(1) 20(1) C(2) ndash607(2) 8055(2) 2630(2) 27(1) C(3) ndash792(2) 6702(2) 3030(2) 29(1) C(4) ndash266(2) 7795(2) 3708(2) 28(1) C(5) 1796(2) 8801(2) 3553(1) 20(1) C(6) 1599(2) 9486(2) 3107(2) 29(1) C(7) 1775(2) 9100(2) 4171(2) 32(1) C(8) 2504(2) 8516(2) 3553(2) 26(1) C(9) 1728(2) 5947(2) 3342(1) 18(1) C(10) 1509(2) 5950(2) 3929(2) 29(1) C(11) 2502(2) 5890(2) 3467(2) 27(1) C(12) 1417(2) 5223(2) 2975(2) 25(1) C(13) 2752(2) 7515(2) 814(1) 26(1) C(14) 2592(2) 8025(2) 1215(1) 23(1) C(15) 2268(2) 7756(2) 1637(1) 24(1) C(16) 2098(2) 6962(2) 1650(2) 26(1) C(17) 2249(2) 6447(2) 1242(2) 28(1) C(18) 2576(2) 6716(2) 837(2) 29(1) C(19) 3117(2) 7803(3) 372(2) 47(1) C(20) 643(2) 5591(2) 680(2) 22(1) C(21) 483(2) 6268(2) 342(2) 25(1) C(22) 153(2) 6897(2) 530(2) 27(1) C(23) ndash7(2) 6865(2) 1072(2) 29(1) C(24) 167(2) 6196(2) 1416(2) 32(1)
155
C(25) 482(2) 5569(2) 1219(2) 28(1) C(26) 985(2) 4905(2) 464(2) 30(1) C(27) ndash355(2) 8950(2) 318(2) 25(1) C(28) ndash296(2) 9000(2) 912(2) 30(1) C(29) 315(2) 9100(2) 1290(2) 35(1) C(30) 887(2) 9143(2) 1079(2) 33(1) C(31) 838(2) 9088(2) 485(2) 33(1) C(32) 224(2) 8995(2) 110(2) 27(1) C(33) ndash1026(2) 8846(2) -97(2) 38(1) Ag(2) 6160(1) ndash2489(1) 1060(1) 25(1) Al(2) 6033(1) ndash2605(1) 2756(1) 15(1) F(29) 6039(1) ndash2337(1) 2075(1) 26(1) F(30) 3522(1) ndash3122(2) 2395(1) 52(1) F(31) 4340(1) ndash3751(2) 2196(1) 60(1) F(33) 4838(1) ndash1420(1) 2412(1) 41(1) F(34) 3847(1) ndash1566(1) 2533(1) 51(1) F(36) 3907(1) ndash2492(2) 3490(1) 55(1) F(37) 4919(2) ndash2812(2) 3838(1) 72(1) F(39) 6834(1) ndash839(1) 2386(1) 41(1) F(40) 5946(1) ndash507(1) 2660(1) 40(1) F(41) 6866(1) 105(1) 3008(1) 38(1) F(42) 6113(1) ndash432(1) 3836(1) 40(1) F(43) 7178(1) ndash345(1) 4144(1) 34(1) F(44) 6662(1) ndash1391(1) 4318(1) 33(1) F(45) 7908(1) ndash908(1) 3378(1) 32(1) F(46) 7715(1) ndash1860(1) 3924(1) 32(1) F(47) 7532(1) ndash2029(1) 3002(1) 36(1) F(48) 6750(1) ndash3316(1) 4026(1) 42(1) F(49) 7669(1) ndash3626(1) 3801(1) 45(1) F(50) 7142(1) ndash4496(1) 4184(1) 43(1) F(51) 6217(1) ndash5360(1) 3427(1) 27(1) F(52) 5735(1) ndash4293(1) 3614(1) 29(1) F(53) 5623(1) ndash4672(1) 2732(1) 28(1) F(54) 7562(1) ndash4169(1) 2709(1) 40(1) F(55) 7465(1) ndash5177(1) 3236(1) 45(1) F(56) 6764(1) ndash4989(1) 2422(1) 39(1) O(4) 5250(1) ndash2848(1) 2834(1) 26(1) O(5) 6337(1) ndash1847(1) 3232(1) 18(1) O(6) 6496(1) ndash3466(1) 2868(1) 19(1) C(34) 4616(2) ndash2641(2) 2821(1) 22(1) F(32A) 4200(3) ndash2688(6) 1821(2) 55(2) F(35A) 4771(3) ndash1342(4) 3275(4) 51(2) F(38A) 4351(3) ndash3672(4) 3419(4) 58(3) C(35A) 4172(4) ndash3053(6) 2324(5) 39(2) C(36A) 4518(4) ndash1712(5) 2778(4) 32(2) C(37A) 4445(6) ndash2888(8) 3419(5) 45(3) F(32B) 4227(3) ndash3935(3) 2992(3) 36(2) F(35B) 4260(3) ndash2182(5) 1827(2) 33(2) F(38B) 4808(4) ndash1695(5) 3544(3) 49(2) C(35B) 4157(4) ndash3397(6) 2579(4) 25(2) C(36B) 4373(4) ndash1956(5) 2371(4) 25(2) C(37B) 4555(6) ndash2419(8) 3412(4) 38(3) C(38) 6762(2) ndash1225(2) 3339(1) 17(1) C(39) 6597(2) ndash602(2) 2842(2) 29(1) C(40) 6679(2) ndash839(2) 3918(2) 25(1) C(41) 7494(2) ndash1504(2) 3414(2) 26(1) C(42) 6674(2) ndash4124(2) 3192(1) 17(1) C(43) 7067(2) ndash3892(2) 3812(2) 31(1) C(44) 6051(2) ndash4623(2) 3241(1) 21(1) C(45) 7123(2) ndash4621(2) 2883(2) 26(1) C(46) 7868(2) ndash2918(2) 707(2) 23(1) C(47) 7543(2) ndash2300(2) 375(2) 30(1)
156
C(48) 7217(2) ndash1725(2) 609(2) 38(1) C(49) 7194(2) ndash1745(2) 1187(2) 36(1) C(50) 7501(2) ndash2368(3) 1528(2) 37(1) C(51) 7843(2) ndash2947(2) 1290(2) 29(1) C(52) 8234(2) ndash3536(2) 444(2) 37(1) C(53) 4909(2) ndash3949(2) 261(2) 27(1) C(54) 4900(2) ndash4013(2) 846(2) 34(1) C(55) 5485(2) ndash4016(2) 1272(2) 38(1) C(56) 6093(2) ndash3951(2) 1121(2) 33(1) C(57) 6109(2) ndash3871(2) 536(2) 31(1) C(58) 5521(2) ndash3872(2) 116(2) 28(1) C(59) 4270(2) ndash3952(2) ndash205(2) 40(1) C(60) 5743(2) ndash469(2) 338(1) 21(1) C(61) 5523(2) ndash1144(2) 16(2) 24(1) C(62) 5214(2) ndash1752(2) 245(2) 31(1) C(63) 5124(2) ndash1705(2) 811(2) 34(1) C(64) 5351(2) ndash1035(2) 1141(2) 32(1) C(65) 5653(2) ndash428(2) 907(1) 26(1) C(66) 6078(2) 196(2) 89(2) 28(1)
157
Table M-10 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(Aring2 x 103) for E-4 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor
x y z U(eq) Al(1) ndash333(1) 2466(1) 1842(1) 20(1) F(1) 94(3) 2225(2) 2619(1) 33(1) F(2) ndash3726(3) 3329(2) 2294(2) 42(1) F(3) ndash4379(3) 3448(2) 1265(2) 42(1) F(4) ndash5304(3) 2626(2) 1828(2) 43(1) F(5) ndash3209(3) 2556(2) 471(1) 34(1) F(6) ndash4792(3) 1878(2) 728(1) 38(1) F(7) ndash2878(3) 1382(2) 785(1) 31(1) F(8) ndash2152(3) 1172(2) 2081(1) 32(1) F(9) ndash4232(3) 1165(2) 1917(1) 36(1) F(10) ndash3195(3) 1857(2) 2691(1) 39(1) F(11) ndash313(4) 232(2) 1542(3) 93(2) F(12) 1201(4) ndash117(2) 1006(2) 78(1) F(13) ndash549(4) 412(3) 514(3) 105(2) F(14) 2407(3) 1903(2) 1943(2) 62(1) F(15) 3123(3) 887(2) 1520(2) 74(1) F(16) 1777(4) 789(2) 2219(2) 79(1) F(17) 2154(5) 2150(2) 663(2) 86(2) F(18) 2054(4) 989(3) 258(2) 85(1) F(19) 394(5) 1727(3) 94(2) 111(2) F(20) 1997(3) 5023(2) 1311(2) 67(1) F(21) 2567(3) 3835(2) 1256(2) 76(1) F(22) 2443(4) 4348(3) 2186(2) 85(2) F(23) ndash1519(4) 4457(2) 1844(3) 85(1) F(24) ndash7(5) 5299(2) 1943(2) 83(1) F(25) 117(5) 4339(3) 2587(2) 106(2) F(26) ndash476(4) 4914(2) 664(2) 70(1) F(27) ndash1329(4) 3817(3) 698(2) 83(1) F(28) 573(5) 3948(3) 382(2) 92(2) O(1) ndash1982(3) 2658(2) 1687(2) 23(1) O(2) -8(3) 1736(2) 1320(2) 27(1) O(3) 472(3) 3302(2) 1697(2) 40(1) C(1) ndash3162(4) 2318(3) 1606(2) 22(1) C(2) ndash4160(5) 2931(3) 1753(3) 30(1) C(3) ndash3526(4) 2031(3) 891(2) 26(1) C(4) ndash3192(5) 1615(3) 2077(2) 28(1) C(5) 915(4) 1247(3) 1160(2) 28(1) C(6) 307(6) 424(4) 1056(4) 60(2) C(7) 2082(5) 1198(4) 1724(3) 43(2) C(8) 1366(7) 1521(4) 534(3) 62(2) C(9) 459(5) 4057(3) 1522(2) 27(1) C(10) 1888(6) 4314(3) 1567(3) 48(2) C(11) ndash223(6) 4554(3) 1989(3) 45(2) C(12) ndash226(6) 4175(4) 815(3) 51(2) C(13) ndash4937(5) 1826(3) ndash1035(2) 23(1) C(14) ndash6282(5) 1807(3) ndash1258(2) 29(1) C(15) ndash6972(5) 1127(3) ndash1253(3) 37(1) C(16) ndash6341(6) 454(3) ndash1018(3) 40(1) C(17) ndash017(6) 451(3) ndash799(3) 37(1) C(18) ndash4307(5) 1131(3) ndash807(2) 28(1) C(19) ndash2899(4) 2537(3) ndash1167(2) 21(1) C(20) ndash2468(5) 1961(3) ndash1567(2) 28(1) C(21) ndash1195(5) 1958(3) ndash1685(2) 33(1) C(22) ndash337(5) 2517(3) ndash1398(3) 38(1) C(23) ndash744(5) 3087(3) ndash1000(3) 34(1) C(24) ndash2014(4) 3099(3) ndash887(2) 26(1)
158
C(25) ndash4855(4) 3265(3) ndash934(2) 22(1) C(26) ndash4577(5) 3946(3) ndash1268(2) 30(1) C(27) ndash5191(5) 4629(3) ndash1165(3) 39(1) C(28) ndash6061(5) 4666(3) ndash722(3) 45(2) C(29) ndash6335(5) 4007(3) ndash381(3) 39(1) C(30) ndash5754(5) 3306(3) ndash495(2) 30(1) C(31) ndash4225(4) 2543(3) ndash1049(2) 21(1)
159
Table M11 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-5 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Ag(2) 1721(1) 3625(1) 7594(1) 40(1) Ag(3) 3309(1) 1365(1) 2366(1) 38(1) C(201) 2032(4) 2365(4) 6900(3) 28(1) C(202) 1281(4) 2918(4) 6883(3) 31(2) C(203) 617(4) 2812(4) 7344(3) 31(2) C(204) 673(4) 2143(4) 7822(3) 28(1) C(205) 1405(4) 1604(3) 7828(3) 31(2) C(206) 2077(4) 1710(4) 7374(3) 27(1) C(207) 1133(5) 5015(4) 6896(3) 39(2) C(208) 1221(5) 5078(3) 7483(3) 37(2) C(209) 510(6) 5041(4) 7910(4) 46(2) C(210) ndash298(5) 4962(4) 7747(3) 39(2) C(211) ndash382(4) 4912(4) 7163(3) 35(2) C(212) 327(5) 4924(3) 6742(3) 33(2) C(213) 2546(5) 2220(5) 8779(3) 43(2) C(214) 2464(4) 3034(5) 8604(4) 45(2) C(215) 3051(4) 3411(4) 8168(3) 36(2) C(216) 3728(4) 2970(4) 7895(3) 33(2) C(217) 3810(4) 2180(4) 8077(3) 28(1) C(218) 3230(4) 1797(4) 8517(3) 35(2) C(301) 1313(4) 1920(4) 2104(3) 26(1) C(302) 1990(4) 1497(4) 1813(3) 29(2) C(303) 2564(4) 1897(4) 1369(3) 36(2) C(304) 2464(4) 2707(4) 1200(3) 36(2) C(305) 1775(4) 3113(4) 1471(3) 31(2) C(306) 1209(4) 2728(4) 1924(3) 26(1) C(307) 3865(4) ndash17(3) 3096(3) 33(2) C(308) 3818(4) ndash85(4) 2505(4) 36(2) C(309) 4556(4) ndash25(4) 2095(3) 36(2) C(310) 5343(4) 89(4) 2282(3) 36(2) C(311) 5380(4) 154(3) 2872(3) 30(2) C(312) 4650(4) 106(4) 3277(3) 32(2) C(313) 2990(4) 2678(4) 3031(3) 31(2) C(314) 3724(4) 2110(4) 3057(3) 26(1) C(315) 4393(4) 2210(4) 2586(3) 29(2) C(316) 4337(4) 2864(3) 2114(3) 27(1) C(317) 3618(5) 3420(3) 2106(3) 29(2) C(318) 2953(4) 3330(4) 2555(3) 30(2) F(205) 1477(3) 961(2) 8283(2) 47(1) F(206) 2776(3) 1167(2) 7403(2) 48(1) F(211) ndash1159(3) 4814(3) 7000(2) 52(1) F(212) 206(3) 4854(3) 6186(2) 58(1) F(217) 4470(2) 1733(2) 7840(2) 40(1) F(218) 3345(3) 1011(2) 8685(2) 46(1) F(305) 1628(3) 3903(2) 1313(2) 42(1) F(306) 555(2) 3158(2) 2173(2) 43(1) F(311) 6130(2) 268(2) 3062(2) 46(1) F(312) 4703(3) 195(2) 3842(2) 47(1) F(317) 3544(3) 4062(2) 1647(2) 50(1) F(318) 2249(3) 3876(2) 2535(2) 51(1) Al(1) 373(1) 802(1) 5195(1) 13(1) Al(2) 4778(1) 4212(1) 4710(1) 15(1) Al(3) 7111(1) 2099(1) 9426(1) 13(1)
160
Al(4) 7903(1) 2871(1) 10541(1) 13(1) C(1) 2272(4) 647(3) 5258(3) 23(1) C(2) 2281(4) 1057(4) 5788(3) 35(2) C(3) 2548(5) 1193(4) 4642(3) 37(2) C(4) 2927(4) ndash124(4) 5357(3) 37(2) C(5) ndash588(3) 732(3) 6415(2) 16(1) C(6) ndash1011(6) 1461(5) 6641(4) 29(2) C(7) 100(5) 238(5) 6846(4) 22(2) C(8) ndash1291(6) 196(5) 6391(4) 26(2) F(10) ndash1737(10) 1745(9) 6364(8) 46(5) F(11) ndash477(5) 2005(3) 6522(3) 29(1) F(12) ndash1190(5) 1266(3) 7257(2) 45(2) F(13) 596(6) 705(5) 7007(4) 28(2) F(14) ndash240(5) ndash193(5) 7352(3) 30(2) F(15) 660(4) ndash236(4) 6563(3) 25(1) F(16) ndash1821(3) 69(4) 6911(3) 44(2) F(17) ndash923(11) ndash505(8) 6417(7) 60(4) F(18) ndash1809(4) 516(4) 5947(3) 28(2) C(6A) ndash145(11) 1212(10) 6810(8) 19(4) C(7A) ndash369(13) ndash156(11) 6679(9) 29(5) C(8A) ndash1562(13) 1008(11) 6439(9) 26(5) F(10A) ndash1823(19) 1788(16) 6402(14) 16(6) F(11A) ndash75(10) 1920(9) 6502(7) 34(4) F(12A) ndash584(8) 1221(6) 7336(5) 26(3) F(13A) 635(15) 926(11) 6923(10) 27(5) F(14A) ndash465(14) ndash325(13) 7304(11) 45(7) F(15A) 421(11) ndash387(10) 6508(8) 31(5) F(16A) ndash1967(7) 667(7) 6983(5) 32(3) F(17A) ndash910(16) ndash540(16) 6290(11) 17(4) F(18A) ndash1914(13) 813(11) 5997(9) 50(6) C(9) ndash309(4) 2259(3) 4361(3) 22(1) C(10) ndash432(5) 2845(4) 4786(3) 35(2) C(11) ndash1209(5) 2022(4) 4276(3) 35(2) C(12) 119(4) 2644(3) 3733(3) 29(2) C(13) 5662(4) 4278(3) 3483(2) 19(1) C(14) 5865(7) 5082(6) 3024(5) 34(3) C(15) 5134(7) 3846(6) 3167(5) 31(3) C(16) 6572(6) 3783(6) 3632(5) 32(3) F(28) 5153(9) 5578(6) 2954(5) 36(2) F(29) 6106(7) 4972(5) 2451(3) 50(2) F(30) 6488(6) 5383(5) 3219(5) 48(3) F(31) 4561(6) 4411(6) 2776(4) 30(2) F(32) 5637(5) 3475(5) 2777(4) 44(2) F(33) 4833(15) 3223(14) 3627(12) 66(7) F(34) 6306(8) 2988(6) 3915(5) 45(3) F(35) 7138(5) 3814(7) 3137(4) 42(2) F(36) 6951(7) 4044(6) 4021(5) 41(3) C(14A) 5210(11) 4775(9) 2891(8) 24(4) C(15A) 5642(11) 3338(9) 3503(8) 24(4) C(16A) 6573(11) 4433(10) 3512(8) 27(4) F(28A) 4951(19) 5503(17) 3001(14) 72(11) F(29A) 5784(11) 4782(9) 2415(8) 50(5) F(30A) 6673(12) 5173(10) 3286(9) 42(5) F(31A) 4446(13) 4335(12) 2944(8) 34(5) F(32A) 5890(11) 3196(9) 2973(8) 54(5) F(33A) 4760(20) 3270(20) 3608(16) 36(7) F(34A) 6477(15) 3025(15) 3794(11) 46(7) F(35A) 7128(16) 4099(13) 3158(12) 79(9) F(36A) 6810(14) 4222(12) 4092(10) 45(6) C(17) 2857(4) 4472(3) 4659(3) 20(1) C(18) 2647(4) 4065(4) 4175(3) 30(2) C(19) 2758(5) 5374(4) 4388(3) 37(2)
161
C(20) 2228(5) 4276(5) 5232(4) 51(2) C(21) 5346(4) 2699(3) 5527(3) 21(1) C(22) 4724(5) 2759(5) 6082(4) 52(2) C(23) 6294(4) 2418(4) 5727(3) 32(2) C(24) 5074(5) 2096(4) 5203(4) 39(2) C(25) 5333(4) 1953(3) 10018(3) 20(1) C(26) 5472(4) 1864(4) 10697(3) 25(2) C(27) 4873(5) 2788(4) 9747(3) 27(2) C(28) 4750(4) 1339(4) 9952(3) 28(2) F(55) 6042(6) 1248(5) 10915(3) 32(2) F(56) 5758(6) 2531(6) 10769(4) 31(2) F(57) 4726(3) 1786(4) 11060(2) 32(1) F(58) 5457(3) 3290(3) 9617(3) 32(1) F(59) 4511(6) 2826(5) 9234(4) 38(2) F(60) 4249(3) 3029(2) 10139(3) 37(1) F(61) 4966(3) 648(3) 10330(3) 36(1) F(62) 4800(5) 1242(5) 9403(4) 41(2) F(63) 3905(3) 1556(4) 10085(2) 36(1) C(26A) 5290(30) 1280(30) 10670(20) 16(11) C(27A) 5210(30) 2780(30) 10320(20) 19(12) C(28A) 4550(30) 2000(30) 9710(20) 20(12) F(55A) 6030(40) 1180(40) 10780(30) 15(12) F(56A) 5940(60) 2450(70) 10750(50) 60(30) F(57A) 4650(30) 1510(20) 11060(20) 19(11) F(58A) 5550(30) 3370(30) 9819(19) 24(11) F(59A) 4410(40) 2630(30) 9270(30) 19(13) F(60A) 4460(20) 3050(20) 10438(19) 33(10) F(61A) 5110(30) 630(20) 10577(19) 28(11) F(62A) 4940(30) 1220(30) 9300(20) 0(8) F(63A) 3810(20) 1940(20) 10041(16) 23(9) C(29) 7096(4) 3084(3) 8177(3) 25(1) C(30) 6437(6) 2679(5) 7955(3) 51(2) C(31) 6829(5) 3994(4) 8036(3) 47(2) C(32) 8014(5) 2916(4) 7852(3) 36(2) C(33) 8050(4) 519(3) 9457(3) 23(1) C(34) 7268(5) 96(4) 9417(4) 39(2) C(35) 8809(5) 319(4) 8999(4) 40(2) C(36) 8352(5) 231(4) 10121(4) 43(2) C(37) 9666(4) 3081(3) 9920(3) 20(1) C(38) 10192(5) 2279(4) 10180(3) 39(2) C(39) 9501(4) 3145(4) 9254(3) 34(2) C(40) 10183(4) 3761(4) 9966(4) 40(2) C(41) 6919(4) 4424(3) 10566(3) 24(1) C(42) 6967(5) 4802(4) 9870(3) 43(2) C(43) 5946(4) 4550(4) 10835(3) 34(2) C(44) 7494(5) 4789(4) 10900(4) 43(2) C(45) 7970(4) 1834(3) 11762(3) 22(1) C(46) 7134(5) 2115(4) 12121(3) 41(2) C(47) 8111(4) 918(4) 11902(3) 31(2) C(48) 8769(6) 2146(5) 11939(4) 52(2) F(1) 2276(3) 550(3) 6322(2) 44(1) F(2) 1566(2) 1592(2) 5787(2) 40(1) F(3) 2971(3) 1457(3) 5723(2) 59(1) F(4) 2344(3) 952(2) 4165(2) 40(1) F(5) 2119(3) 1927(2) 4607(2) 45(1) F(6) 3402(3) 1243(3) 4571(2) 47(1) F(7) 3698(2) 3(3) 5511(2) 52(1) F(8) 3067(3) -388(2) 4846(2) 47(1) F(9) 2624(2) -668(2) 5811(2) 43(1) F(19) 307(3) 2866(2) 5017(2) 51(1) F(20) ndash1018(3) 2642(2) 5249(2) 41(1) F(21) ndash715(3) 3574(2) 4483(2) 55(1)
162
F(22) ndash1474(2) 1509(2) 4768(2) 38(1) F(23) ndash1825(3) 2639(3) 4177(2) 51(1) F(24) ndash1153(3) 1692(2) 3802(2) 46(1) F(25) ndash452(3) 3156(2) 3384(2) 43(1) F(26) 459(3) 2108(2) 3422(2) 41(1) F(27) 764(3) 3029(2) 3791(2) 47(1) F(37) 2954(3) 3315(2) 4299(2) 49(1) F(38) 2997(3) 4383(2) 3619(2) 48(1) F(39) 1793(3) 4104(3) 4127(2) 64(1) F(40) 3459(3) 5565(2) 4012(2) 49(1) F(41) 2734(4) 5755(3) 4834(2) 73(2) F(42) 2052(3) 5637(2) 4086(2) 58(1) F(43) 2142(3) 3510(3) 5372(2) 57(1) F(44) 2516(4) 4431(3) 5712(2) 72(2) F(45) 1430(3) 4685(4) 5142(3) 91(2) F(46) 3885(3) 2802(3) 5955(2) 74(2) F(47) 4782(4) 3418(3) 6257(2) 80(2) F(48) 4857(4) 2172(3) 6558(2) 87(2) F(49) 6482(3) 2801(2) 6122(2) 49(1) F(50) 6873(2) 2522(2) 5263(2) 48(1) F(51) 6389(3) 1645(2) 6003(2) 51(1) F(52) 4850(3) 1452(2) 5606(3) 70(2) F(53) 4393(3) 2408(2) 4885(2) 60(1) F(54) 5712(3) 1857(3) 4829(2) 63(1) F(64) 6826(4) 1915(3) 7943(3) 92(2) F(65) 5767(4) 2585(6) 8312(2) 140(4) F(66) 6226(3) 2964(3) 7397(2) 64(1) F(67) 6014(4) 4141(3) 8235(2) 110(3) F(68) 7302(5) 4344(3) 8304(3) 87(2) F(69) 6868(3) 4301(3) 7434(2) 68(2) F(70) 7994(3) 3026(2) 7250(2) 45(1) F(71) 8560(3) 3403(3) 7936(2) 64(1) F(72) 8406(3) 2227(3) 8083(2) 59(1) F(73) 6707(3) 61(2) 9920(2) 47(1) F(74) 6813(3) 468(3) 8944(2) 63(1) F(75) 7520(3) -647(2) 9366(2) 63(1) F(76) 8475(3) 382(2) 8453(2) 59(1) F(77) 9383(3) 806(2) 8900(3) 64(2) F(78) 9198(3) -407(2) 9152(2) 52(1) F(79) 8395(3) -537(2) 10322(2) 62(1) F(80) 9151(3) 414(3) 10139(3) 73(2) F(81) 7821(3) 570(3) 10498(2) 59(1) F(82) 10580(2) 2295(2) 10676(2) 43(1) F(83) 9661(3) 1722(2) 10317(2) 44(1) F(84) 10816(3) 2079(2) 9763(2) 59(1) F(85) 10220(3) 3296(2) 8866(2) 41(1) F(86) 9245(2) 2469(2) 9186(2) 35(1) F(87) 8876(3) 3737(2) 9063(2) 39(1) F(88) 9848(3) 4434(2) 9603(2) 49(1) F(89) 10146(3) 3827(2) 10540(2) 42(1) F(90) 11026(3) 3600(3) 9785(2) 61(1) F(91) 6707(4) 4361(3) 9562(2) 76(2) F(92) 7822(3) 4856(3) 9687(2) 75(2) F(93) 6563(3) 5517(2) 9734(2) 62(1) F(94) 5414(3) 4372(3) 10475(2) 60(1) F(95) 5706(3) 5294(2) 10873(2) 53(1) F(96) 5829(3) 4091(2) 11372(2) 45(1) F(97) 7396(3) 5573(2) 10727(2) 62(1) F(98) 7294(3) 4610(3) 11518(2) 60(1) F(99) 8324(3) 4529(3) 10832(3) 67(2) F(100) 7082(5) 2884(3) 12068(2) 101(2) F(101) 6437(3) 1976(4) 11923(2) 83(2)
163
F(102) 7126(3) 1803(3) 12718(2) 56(1) F(103) 7404(3) 649(2) 11811(2) 57(1) F(104) 8758(3) 664(2) 11551(2) 57(1) F(105) 8285(3) 615(2) 12480(2) 59(1) F(106) 8840(3) 2021(3) 12523(2) 74(2) F(107) 9518(3) 1785(4) 11719(2) 87(2) F(108) 8790(4) 2891(3) 11665(3) 91(2) F(201) 0 0 5000 16(1) F(202) 5000 5000 5000 17(1) F(203) 7504(2) 2497(2) 9974(1) 16(1) O(1) 1461(2) 447(2) 5234(2) 22(1) O(2) -229(2) 958(2) 5837(2) 18(1) O(3) 230(3) 1598(2) 4601(2) 22(1) O(4) 5192(3) 4467(3) 3970(2) 35(1) O(5) 3686(3) 4212(2) 4817(2) 32(1) O(6) 5351(3) 3402(2) 5126(2) 28(1) O(7) 6116(2) 1818(2) 9712(2) 20(1) O(8) 7150(3) 2849(2) 8793(2) 21(1) O(9) 7830(2) 1303(2) 9334(2) 23(1) O(10) 8890(2) 3160(2) 10252(2) 19(1) O(11) 7161(2) 3636(2) 10664(2) 21(1) O(12) 7883(2) 2086(2) 11151(2) 20(1)
164
Table M-12 Atomic coordinates (x 104) and equivalent isotropic displacement parameters
(pm2 x 10ndash1) for E-6 U(eq) is defined as one third of the trace of the orthogonalized Uij
tensor
x y z U(eq) Al(1) 136(2) 9182(1) 2772(1) 34(1) O(1) ndash1157(3) 9063(3) 3076(2) 40(1) F(1) ndash2105(4) 8289(3) 3958(2) 69(1) C(1) ndash2048(5) 9423(4) 3327(3) 39(1) Al(2) 328(1) 7494(1) 1819(1) 32(1) O(2) ndash25(4) 9891(3) 2184(2) 42(1) F(2) ndash1221(5) 9295(4) 4517(2) 91(2) C(2) ndash2198(9) 9019(6) 3986(5) 80(3) Al(3) 452(1) 5765(1) 2731(1) 33(1) O(3) 1528(4) 9276(3) 3336(2) 42(1) F(3) ndash3268(4) 9194(3) 4130(2) 72(1) C(3) ndash1663(8) 10257(6) 3525(5) 86(3) O(4) 1695(3) 7657(3) 1613(2) 38(1) F(4) ndash1932(5) 10664(3) 2865(3) 98(2) C(4) ndash3257(7) 9391(7) 2784(4) 89(4) O(5) ndash1036(3) 7329(3) 1251(2) 38(1) F(5) ndash2355(4) 10594(3) 3887(2) 65(1) C(5) 539(6) 10454(4) 1890(3) 45(2) F(6) ndash521(4) 10363(3) 3779(3) 71(1) O(6) 461(3) 5137(3) 2090(2) 40(1) C(6) 727(16) 11180(7) 2340(5) 146(5) O(7) 1818(3) 5816(3) 3328(2) 39(1) F(7) ndash3750(4) 8617(4) 2821(3) 100(2) C(7) ndash290(9) 10598(8) 1181(6) 145(5) O(8) ndash877(3) 5688(3) 3002(2) 39(1) F(8) ndash3167(4) 9483(3) 2173(2) 72(1) C(8) 1782(11) 10194(7) 1817(8) 132(4) C(9) 2403(5) 8986(4) 3854(3) 40(2) F(9) ndash4100(4) 9889(4) 2914(2) 82(2) C(10) 3248(6) 9649(5) 4216(3) 52(2) F(10) 944(5) 11097(3) 2955(2) 83(2) C(11) 3186(6) 8411(5) 3554(3) 52(2) F(11) 1465(5) 11707(3) 2144(3) 89(2) C(12) 1798(6) 8581(4) 4369(3) 48(2) F(12) ndash635(7) 11515(4) 2086(5) 160(3) C(13) 2558(5) 7353(4) 1300(3) 41(2) F(13) ndash1423(4) 10531(3) 1124(2) 77(1) C(14) 1928(6) 6893(5) 667(4) 60(2) F(14) ndash6(4) 11264(3) 914(2) 83(2) C(15) 3307(8) 8030(7) 1100(4) 82(3) F(15) 107(9) 9941(5) 770(3) 151(4) C(16) 3414(7) 6813(7) 1821(4) 74(3) F(16) 2250(4) 10578(3) 1360(2) 76(1) C(17) ndash1949(5) 7644(4) 745(3) 37(1) F(17) 1924(4) 9472(3) 1770(2) 73(1) C(18) ndash2857(6) 6990(5) 419(3) 53(2) F(18) 2632(5) 10441(4) 2513(3) 132(3) F(19) 3925(4) 9454(3) 4823(2) 77(1) C(19) ndash1384(6) 8030(5) 209(3) 52(2) F(20) 2564(4) 10253(3) 4310(2) 63(1) C(20) ndash2636(6) 8243(5) 1077(3) 46(2) F(21) 4015(4) 9905(3) 3839(2) 62(1) C(21) ndash105(5) 4550(4) 1677(3) 41(2)
165
F(22) 4218(4) 8210(3) 4001(2) 68(1) F(23) 3501(4) 8700(3) 3010(2) 64(1) F(24) 2510(4) 7763(2) 3344(2) 59(1) C(25) 2695(5) 5445(4) 3799(3) 39(2) F(25) 2567(4) 8143(3) 4813(2) 62(1) F(26) 864(4) 8126(3) 4044(2) 60(1) C(26) 3588(6) 6048(5) 4208(3) 53(2) F(27) 1326(4) 9087(3) 4729(2) 64(1) C(27) 2086(6) 4976(4) 4287(3) 47(2) C(28) 3427(6) 4896(5) 3434(3) 48(2) F(28) 2668(4) 6365(3) 485(2) 72(1) F(29) 1513(4) 7365(3) 131(2) 66(1) C(29) ndash1739(5) 6000(4) 3310(3) 36(1) F(30) 947(4) 6497(3) 789(2) 63(1) C(30) ndash2694(6) 5362(5) 3368(3) 47(2) C(31) ndash1108(6) 6299(4) 4032(3) 45(2) F(31) 4098(4) 8312(4) 1661(3) 94(2) C(32) ndash2388(6) 6653(4) 2866(3) 45(2) F(32) 3982(5) 7757(4) 670(3) 102(2) F(33) 2572(5) 8562(3) 772(3) 82(1) F(34) 2738(5) 6146(3) 1853(3) 79(1) F(35) 4425(4) 6650(4) 1614(2) 96(2) F(36) 3748(4) 7142(3) 2416(2) 75(2) F(37) ndash3599(4) 7229(3) ndash162(2) 64(1) F(38) ndash2239(4) 6394(3) 266(2) 58(1) F(39) ndash3567(3) 6761(3) 821(2) 55(1) F(40) ndash2124(4) 8547(3) ndash158(2) 68(1) F(41) ndash1100(4) 7517(3) ndash222(2) 59(1) F(42) ndash330(3) 8410(3) 509(2) 57(1) F(43) ndash2908(4) 7984(2) 1640(2) 52(1) F(44) ndash3689(3) 8473(3) 661(2) 56(1) F(45) ndash1902(3) 8876(2) 1255(2) 54(1) F(46) ndash486(8) 3206(3) 1708(3) 120(3) F(47) 328(4) 3770(3) 2653(2) 72(1) F(48) 1538(4) 3672(3) 1888(2) 72(1) F(49) -527(5) 5186(3) 607(2) 70(1) F(50) 85(4) 3934(3) 646(2) 86(2) F(51) 1425(3) 4794(3) 1058(2) 56(1) F(52) ndash1811(4) 4280(3) 2150(2) 76(1) F(53) ndash2098(4) 4200(3) 975(2) 82(2) F(54) ndash1895(4) 5322(3) 1448(2) 65(1) F(55) 4320(4) 5768(3) 4770(2) 73(1) F(56) 2963(4) 6622(3) 4415(2) 60(1) F(57) 4300(4) 6367(3) 3836(2) 65(1) F(58) 1775(4) 5436(3) 4752(2) 67(1) F(59) 2836(4) 4436(3) 4623(2) 62(1) F(60) 1056(3) 4627(3) 3941(2) 61(1) F(61) 4469(3) 4652(3) 3849(2) 60(1) F(62) 3720(4) 5229(3) 2912(2) 70(1) F(63) 2743(4) 4272(3) 3204(2) 68(1) F(64) ndash2122(4) 4711(3) 3586(2) 59(1) F(65) ndash3467(3) 5216(3) 2763(2) 65(1) F(66) ndash3358(4) 5568(3) 3806(2) 63(1) F(67) ndash1834(4) 6763(3) 4285(2) 56(1) F(68) ndash62(4) 6674(3) 4019(2) 55(1) F(69) ndash799(4) 5723(3) 4469(2) 57(1) F(70) ndash3409(3) 6880(3) 3049(2) 58(1) F(71) ndash1608(4) 7268(2) 2918(2) 57(1) F(72) ndash2701(4) 6459(3) 2215(2) 60(1) F(100) 447(3) 6701(2) 2354(1) 35(1) F(101) 184(3) 8277(2) 2337(1) 35(1) C(101) 3950(6) 7962(5) 7860(3) 51(2)
166
C(102) 4952(7) 8424(5) 8348(3) 59(2) C(103) 4349(9) 8888(7) 8830(5) 86(3) C(104) 5051(13) 9542(10) 9213(8) 143(6) C(105) 5023(6) 7905(4) 6914(3) 47(2) C(106) 5352(7) 7466(5) 6328(4) 53(2) C(107) 6009(8) 8014(5) 5939(4) 60(2) C(108) 6420(8) 7611(6) 5361(4) 67(2) C(109) 5269(5) 6841(4) 7743(3) 45(2) C(110) 4832(5) 6391(4) 8287(3) 45(2) C(111) 5815(7) 5816(5) 8622(3) 53(2) C(112) 5375(8) 5325(5) 9142(4) 64(2) C(113) 3243(5) 7000(4) 6926(3) 46(2) C(114) 2233(7) 7506(5) 6520(3) 57(2) C(115) 1177(7) 7018(5) 6091(4) 63(2) C(116) 94(7) 7513(7) 5763(4) 75(3) N(1) 4373(5) 7424(4) 7368(3) 46(1) C(22) 376(10) 3759(6) 1984(5) 52(3) C(23) 240(9) 4646(6) 964(5) 46(3) C(24) ndash1524(9) 4594(7) 1550(5) 50(3) C(22A) ndash610(20) 3964(14) 2116(13) 56(6) C(23A) 790(20) 4168(16) 1318(9) 64(8) C(24A) ndash1220(19) 4834(14) 1122(13) 55(7)
167
N Publications
bull PX4+ P2X5
+ and P5X2+ (X=Br I) salts of the superweak Al(OR)4
--anion [R=C(CF3)3]
M Gonsior I Raabe L Muumlller J Martin L v Wuumlllen I Krossing Chemistry 2002
8(19) 4475-92
bull Patent Method for the production of salts of weakly fluorinated alcoholato
complex anions of main group elements M Gonsior L Muumlller I Krossing PCT
Int Appl 2005 WO 2005054254 A1 20050616
bull Chasing an elusive alkoxide attempts to synthesize [OC(tert-Bu)(CF3)2]-
L O Muumlller R Scopelliti I Krossing Chimia 2006 60(4) 220-223
bull Lewis acid stabilized OPI3 implications for the nature of free OPI3 M Gonsior
L Muumlller I Krossing Chemistry 2006 12(22) 5815-5822
bull A hexane soluble lithium salt of a fluorinated weakly coordinating anion
Li[Al(OC(CF3)2(CH2SiMe3))4] L O Muumlller I Krossing Z Anorg Allg Chem
in press
bull Structural variations of new fluorinated Lithiumalkoxides and attempts to
prepare new WCAs from them L O Muumlller R Scopelitti I Krossing
Z Anorg Allg Chem in press
bull Lewis Superacidity A Definition Simple Access to the Non-Oxidizing Superacid
PhndashFrarrAl(ORF)3 (RF = C(CF3)3) L O Muumlller D Himmel J Stauffer G Steinfeld J
Slattery V Brecht I Krossing publication in progress
168
bull The Chemistry of the Lewis Superacid Al(ORF)3 and its conjugated anion
[FAl(ORF)3]- (RF = C(CF3)3) L O Muumlller J Stauffer G Santiso D Himmel
R Scopelitti I Krossing publication in progress
169
O Lectures conferences and posters 092007 Definition of Lewis Superacidity and Simple Access to the
Non-Oxidizing Lewis Superacid Ph-FrarrAl(ORF)3 (RF = C(CF3)3) G Steinfeld L O Muumlller D Himmel J Stauffer V Brecht I Krossing GdCh Jahrestagung Chemie Ulm (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2007 -) 072007 Die Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3) G Steinfeld
L O Muumlller I Krossing Tag der Forschung Albert-Ludwigs-Universitaumlt Freiburg
092006 Zur Chemie der Lewis Super Saumlure Al(ORF)3 (RF = C(CF3)3)
L O Muumlller I Krossing 12 Deutscher Fluortag Schmitten
102005 Development of new Weakly Coordinating Anions (WCAs)
L O Muumlller R Scopelliti I Krossing SCS ndash Fall Meeting
Lausanne (- Award in Best poster presentation in Inorganic and
Coordination Chemistry 2005 -)
092005 Synthesis attempts to new Weakly Coordinating (per-)fluorinated
Anions Al(ORF)4- L O Muumlller R Scopelliti I Krossing GdCh
Hauptversammlung Duumlsseldorf
092004 11 Deutscher Fluortag Schmitten