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 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
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