Evidence for SO2, C2H4Cl2 and CH2Cl2 soluble salts of bismuth homopolyatomic cations and [Bi4OF2Cl6(C6Me6) 4

Article abstract of DOI:10.1016/j.poly.2005.06.032

Evidence is presented that the SO₂, C₂H ₄Cl₂ and CH₂Cl₂ soluble salts of composition [Bi_x][Al(OC(CF₃)₃) ₄]₃ (1), x close to 4.33, and [Bi₅(C ₆Me₆)₄][Al(OC(CF₃)₃) ₄]₃ (2), have been prepared in moderate yields by the metathesis reaction of [Bi₅][AsF₆]₃ and Li[Al(OC(CF₃)₃)₄] in SO₂, and in CH₂Cl₂ in the presence of C₆Me₆, respectively. The compositions of 1 and 2 are supported by elemental analysis, IR, NMR and EI-MS. The UV-Vis spectra of 1 and 2 in SO₂ and C ₂H₄Cl₂ were consistent with the presence of the bismuth cations [Bi₅]³⁺, [Bi₈]²⁺, [Bi]⁺ and possibly [Bi₉]⁵⁺. The 1:2 salt [Bi₄OF₂Cl₆(C₆Me₆) ₄][Al(OC(CF₃)₃)₄] ₂·C₆Me₆ (3·C₆Me ₆) was isolated from a solution of 2, and characterized by preliminary X-ray crystal structure, NMR and IR. Complex 3 contains a discrete oxygen-centered fluorine and chlorine-bridged bismuth cluster [Bi ₄OF₂Cl₆]²⁺ with each bismuth weakly coordinated to hexamethylbenzene.

Full text of DOI:10.1016/j.poly.2005.06.032

Polyhedron 24 (2005) 2994–3003
www.elsevier.com/locate/poly
Evidence for SO2, C2H4Cl2 and CH2Cl2 soluble salts
of bismuth homopolyatomic cations and
[Bi4OF2Cl6(C6Me6)4][Al(OC(CF3)3)4]2 Æ C6Me6,
containing the novel [Bi4OF2Cl6]2+ cation
*
Andreas Decken, Grigori B. Nikiforov, Jack Passmore
Chemistry Department, University of New Brunswick, 30 Dineen Drive, Fredericton, NB, Canada E3B 6E2
Received 17 March 2005; accepted 22 June 2005
Available online 26 August 2005
Abstract
Evidence is presented that the SO2, C2H4Cl2 and CH2Cl2 soluble salts of composition [Bix][Al(OC(CF3)3)4]3 (1), x close to 4.33,
and [Bi5(C6Me6)4][Al(OC(CF3)3)4]3 (2), have been prepared in moderate yields by the metathesis reaction of [Bi5][AsF6]3 and Li[Al-
(OC(CF3)3)4] in SO2, and in CH2Cl2 in the presence of C6Me6, respectively. The compositions of 1 and 2 are supported by elemental
analysis, IR, NMR and EI-MS. The UV–Vis spectra of 1 and 2 in SO2 and C2H4Cl2 were consistent with the presence of the bismuth
cations [Bi5]3+, [Bi8]2+, [Bi]+ and possibly [Bi9]5+. The 1:2 salt [Bi4OF2Cl6(C6Me6)4][Al(OC(CF3)3)4]2 Æ C6Me6 (3 Æ C6Me6) was iso-
lated from a solution of 2, and characterized by preliminary X-ray crystal structure, NMR and IR. Complex 3 contains a discrete
oxygen-centered fluorine and chlorine-bridged bismuth cluster [Bi4OF2Cl6]2+ with each bismuth weakly coordinated to
hexamethylbenzene.
ꢀ 2005 Elsevier Ltd. All rights reserved.
Keywords: Weakly coordinating anion; Bismuth homopolyatomic cation; Aluminium; C–F, C–Cl bond activation
1. Introduction
During the last three decades we have discovered a
rich chemistry of the polyatomic cations of main group
elements [8]. A wide range of salts containing novel cat-
ions, e.g., sulfur and selenium halide cations [M2I4]2+
M = S, Se [9], [M3X3]+ X = Cl, Br, I [10], [S7X]+ [11],
[Se6I2]2+ [12], and heterocyclic compounds [(CNSSS)2]2+
[13], [(CNSSS)2]2+ꢀꢀ [14], [CF3CNSSS]+ꢀ [15] and
[F3CCSSSCCF3]+ [16] that possess novel electronic
and magnetic properties have been obtained from reac-
tions of homopolyatomic cations of group 16 and 17 in
the solvent SO2. One aim of this work was the prepara-
tion of soluble salts of bismuth homopolyatomic cations
as precursors to new bismuth containing compounds.
In order to prepare soluble salts of bismuth polyatomic
cations, we investigated the reaction of [Bi5][AsF6]3 and
Li[Al(OC(CF3)3)4] in the solvents (a) SO2, (b) CH2Cl2 in
the presence of the molecular donor ligand C6Me6. We
Bismuth homopolyatomic cations have been studied
extensively during the last 30 years. A number of salts
containing [Bi]+ [1], [Bi2]4+ [2], [Bi5]+ [3], [Bi5]3+ [4],
[Bi6]2+ [3], [Bi8]2+ [1a,4a,5] and [Bi9]5+ [1a,1b,1c,5a,6]
cations have been synthesized either by molten and solid
state routes or in SO2 or in superacid systems [1–6]. The
resulting salts are insoluble, [Bi5][AsF6]3 having very low
solubility in SO2, thus, restricting the further explora-
tion of their chemistry. The subvalent bismuth cations
including [Bi5]3+ and [Bi]+ have been observed in In–
BiCl3–GaCl3–benzene and Bi–GaCl3–benzene solutions
[7], from which [Bi5][GaCl4]3 was isolated.
*
Corresponding author. Tel./fax: +1 506 453 48 21.
E-mail address: passmore@unb.ca (J. Passmore).
0277-5387/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.06.032

A. Decken et al. / Polyhedron 24 (2005) 2994–3003
2995
The bismuth containing product is very soluble in
SO2 and contains [Al(OC(CF3)3)4]ꢀ anion [19F, 27Al
NMR] showing that the anion has remained a spectator
anion. The UV–Vis spectrum contained the band max-
ima (Table 1, column 2, actual spectra see S.I.) at 405,
450, 523 nm (Table 1) and 347 nm (shoulder) close to
those of [Bi5]3+, [Bi8]2+ and probably [Bi9]5+ cations
(Table 1) (a full interpretation of the UV spectra of
[Bi5]3+, [Bi8]2+, [Bi9]5+ is given in [20]). The digital
Gaussian deconvolution of the UV–Vis spectrum
yielded the relative intensities of the bands allowing to
calculate the molar absorptivities 5.1 · 103 (409 nm),
4.6 · 103 (453 nm), 3.1 · 103 (517 nm), 1 · 102 (804 nm),
which are in agreement with the literature data for the
[Bi5]3+ or [Bi8]2+ [24,7b,26]. Resolved bands arising
from the presence of [Bi]+ cation were not detected,
however, a better fit of the calculated curve was ob-
tained by postulating a weak band of [Bi]+ 677 nm
superimposed upon the more intense [Bi5]3+ (or
[Bi8]2+) absorptions
F
O
Bi
Cl
Cl(4)
Bi(4)
Cl(2)
F(3)
Cl(6)
Bi(2)
Cl(5)
Bi(1)
O(1)
Bi(3)
F(2)
Cl(3)
Cl(1)
Fig. 1. The crystal structure of the {[Bi4OF2Cl6](C6Me6)4}2+ cation.
found that the [Bi5][AsF6]3 salt has sufficient solubility in
SO2 for the [17] metathesis reaction, replacing the [AsF6]ꢀ
anion (0.110 nm3 [18]) by the larger [Al(OC(CF3)3)4]ꢀ an-
ion (0.758 nm3 [19]). The estimated lattice energy of the
[Bi5][Al(OC(CF3)3)4]3 of 1571 kJ/mol is about 900 kJ/
mol lower than that of the [Bi5][AsF6]3 2467 kJ/mol1
and is therefore comparable in energy to those of the
SO2 soluble salts containing homopolyatomic cations of
SO2;r:t:
3þ
3½Bi5ꢁ
¢ ½Bi8ꢁ2þ þ 7½Biꢁþ
ð2Þ
2½Bi5ꢁ3þ ¢ ½Bi9ꢁ5þ þ ½Biꢁþ
Thus, the SO2 solution of the reaction product con-
tained a mixture [Bi5]3+, [Bi8]2+, [Bi9]5+ and the [Bi]+.
The given cations could be generated by Eqs. (2) from
the [Bi5]3+. We note that [Sb8][GaCl4] was isolated from
solutions of SbCl3 in the Ga–GaCl3–benzene system
[21], whereas previously [Bi5]3+ and [Bi]+ have been ob-
served in Bi–GaCl3–benzene solutions [7] and a products
suggested to be [M5][GaCl4]3 (M = Sb, Bi) were isolated
from the MCl3–Ga–GaCl3 molten salt systems [4c].
The major IR absorption bands of the reaction prod-
ucts are due to the nonafluorobutoxide ligands. The
bands at 832, 864 cmꢀ1, which are not observed in the
spectrum of Li[Al(OC(CF3)3)4] have been assigned [22]
to the Al–O vibrations of 1. Energies of these bands
are close to those of Li[Al(OC(CF3)3)4] (S.I., Section 2)
with differences ca. 10 cmꢀ1. Thus, the local geometry
around the Al atom in 1 is distorted and lower symmetry
than tetrahedral, much like that in the Li[Al-
(OC(CF3)3)4], as the bismuth cation could have strong
Bi–F and Bi–O contacts reminiscent of those of [Li]+
in Li[Al(OC(CF3)3)4]2 [23].
group 16, e.g., UPOT([S4][AsF6]2) = 1557 kJ/mol, UPOT
-
([Se4][AsF6]2) = 1544 kJ/mol, [Te4][AsF6]2, 1518 kJ/mol.1
2. Results and discussion
2.1. Reaction of [Bi5][AsF6]3 and Li[Al(OC(CF3)3)4]
in SO2
The reaction of SO2 soluble Li[Al(OC(CF3)3)4] and
NO[SbF6] [17] gave the insoluble Li[SbF6] (s) and
NO[Al(OC(CF3)3)4]. In contrast the corresponding reac-
tion of Li[Al(OC(CF3)3)4] and excess of the weakly sol-
uble [Bi5][AsF6]3 afforded insoluble Li[AsF6] and the
reaction product [Bix][Al(OC(CF3)3)4]3 (1), x close to
4.33 according to the elemental analysis (Eq. (1)), con-
taminated with 10% of starting material Li[Al-
7
(OC(CF3)3)4], determined by quantitative Li NMR
3Li½AlðOCðCF3Þ3Þ4ꢁ þ ½Bi5ꢁ½AsF6ꢁ3
2.2. Reaction of [Bi5][AsF6]3 with Li[Al(OC(CF3)3)4]
and C6Me6 in CH2Cl2
SO2;r:t:
½Bi ꢁ½AlðOCðCF Þ Þ ꢁ þ 3Li½AsF ꢁðsÞ
ð1Þ
ꢀꢀ!
x
3
6
3
4 3
The metathesis reaction of [Bi5][AsF6]3 and Li[Al(OC-
(CF3)3)4] in the presence of C6Me6 in CH2Cl2 yields dark
brown, Li[Al(OC(CF3)3)4] free, highly soluble regularly
1
Lattice energies have been calculated using the volume-based
equation given in [18]. Volume of [Bi5]3+ 0.143 nm3 was obtained by
subtracting the three volumes of [AlCl4]ꢀ anion 0.156 nm3 from the
molecular volume of the [Bi5][AlCl4]3 0.611 nm3 [4b]. Volume of the
[AsF6] was taken from [18], lattice energies of [M4][AsF6]2 M = S, Se,
Te were taken from [18].
2
[Li]+ in the Li[Al(OC(CF3)2Ph)4] [23a] and Li[Al(OC(CF3)3)4] [23b]
is coordinated to the 2 oxygen and 4 fluorine atoms of the ligand,
lowering the local symmetry around aluminium atom from Td to C2v
.

2996
A. Decken et al. / Polyhedron 24 (2005) 2994–3003
shaped crystals, which did not diffract X-rays. The reac-
tion product is interpreted as a salt containing the
[Bi5]3+ cation, e.g., [Bi5(C6Me6)4][Al(OC(CF3)3)4]3 (2)
based on the elemental analysis (Eq. (3))
3Li½AlðOCðCF3Þ3Þ4ꢁ þ ½Bi5ꢁ½AsF6ꢁ3 þ 4C6Me6
CH2Cl2
! ½Bi ðC Me Þ ꢁ½AlðOCðCF Þ Þ ꢁ þ 3Li½AsF ꢁ
ꢀꢀꢀ!
5
6
6
3
6
4
3 4 3
þ5 ꢂC
2
ð3Þ
The UV–Vis spectrum (Table 1, spectrum is shown in
the S.I. Figs. 8 and 9) of 2 in C2H4Cl2 was consistent
with [Bi5]3+, [Bi8]2+, [Bi9]5+ cations in solution as well
as [Bi]+. Reported band maxima of [Bi5]3+ and [Bi8]2+
and that at 450 nm for the [Bi9]5+ are close to each
other, hence these cations might be in equilibrium with
2 (Eq. (2)) in C2H4Cl2. The molar absorptivities of
[Bi5]3+ in 2 are in the same range but higher, as those
of [Bi5]3+ in NaCl–AlCl3 melts, strongly supporting
our assignment of the bands to [Bi5]3+ and the presence
of [Bi]+, [Bi8]2+ and probably [Bi9]5+
.
The IR absorption bands of C6Me6 in 2 are slightly
shifted from those of C6Me6 (Tables 2 and 3), implying
weak interaction between the bismuth cation and
C6Me6. In addition, the IR spectrum contains only
one Al–O band 832 cmꢀ1 in the range 800–900 cmꢀ1
[22] consistent with Td site symmetry around the alumin-
ium atom and very weak cation–anion interaction in 2.
2.3. Evidence for [Bi4OF2Cl6(C6Me6)4]-
[Al(OC(CF3)3)4]2 Æ C6Me6
Crystals of 2 {[Bi5(C6Me6)4][Al(OC(CF3)3)4]3} were
deposited from the reaction mixture during a period of
1–6 days. For the next 10 days, crystals of 2 were con-
taminated with yellow crystals assigned to 3 and
[C6Me6H][Al(OC(CF3)3)4]3 and after an additional 5
days only yellow and orange crystals of 3, [C6Me6H][Al-
(OC(CF3)3)4] and colourless crystals4 were obtained.
We propose that the homopolyatomic cations gener-
ated in the metathesis reaction in CH2Cl2 are very chem-
3
Yellow crystals 4 refined in C1, a = 9.825, b = 20.046, c = 21.148,
a ꢃ b ꢃ c ꢃ 90ꢁ, Z = 2 to the R factor close to 25% and was consistent
with the presence of [Al(OC(CF3)3)4]ꢀ and {C6Me6} or ([C6Me6H]+)
moieties. Problem of disordering –C(CF3)3 groups in the anion
precluded further refinement. It could be Li[Al(OC(CF3)3)4] Æ C6Me6
or [C6Me6H][Al(OC(CF3)3)4]. A 7Li resonance was not observed at r.t.
and low temperature for the solution of yellow reaction product, hence
[C6Me6H][Al(OC(CF3)3)4] formulation seems to be more feasible,
additional IR evidence of [C6Me6H]+ is described in Section 4.
4
Colourless crystals that deposits from solution in a period of 1
month at ꢀ24 ꢁC refined in C1, a = 14.330(2), b = 18.114(3),
c = 22.492(4), a = 84.252(2), b = 72.851(2), c = 82.616(2), Z = 4 to
the R factor close to 20%. The proposed structure obtained at this
ꢀ
point of refinement consistent of [Al(OC(CF3)3)4]ꢀ and [Al7O4F14
]
and/or [Al7O3F15] moieties. Problem of disordering –C(CF3)3 groups
in the anion precluded further refinement.

A. Decken et al. / Polyhedron 24 (2005) 2994–3003
2997
Table 2
[30] (e.g., for CHCl3 by the rhodium complex LRh(CO)2
L = tris(3,5-dimethyl,4-chloropyrazolyl)borate [30a]).
The salt 3 Æ C6Me6 (Fig. 1) is the first example of a 1:2
salt of the bulky polyfluoroalkoxyaluminate anion, the
first example of a discrete oxygen-centered tetrahedral
arrangement of group 15, and a rare example of a Bi(III)
fluoride complex [31,32]. Four-coordinate oxygen cen-
ters have been reported in bismuth alkoxide clusters
having complex oligomeric structures (i.e., Bi4(l4-O)-
(l-OR)6{l3-OBi(l-OR)3}2(C6H5CH3)) [33] as well as
for main group [34,35], d-block [36,37] and f-block
[38,39] metal complexes. The structure of 3 Æ C6Me6
was obtained from crystals of poor quality, albeit many
unsuccessful attempts made to improve their quality.
However, the connectivity in [Bi4OF2Cl6]2+ has been
established and the data clearly show the presence of
C6Me6 and the [Al(OC(CF3)3)4]ꢀ anion. The quality of
the X-ray structure does not allow unambiguous assign-
ment of the bridging light atoms as oxygen or fluorine
within the Bi4X2Cl4Y core and the atom type assign-
ment has been made based on chemical arguments –
bond valence theory, ESR and NMR data. The sum
of four Bi–O(1) contacts is 2.17 v.u. and consistent with
a valence of 2 for oxygen, while four Bi–(F1) contacts
would give 1.64 v.u.6 [40] for fluorine, strongly support-
ing the assignment of the central atom as oxygen. In
addition, a Bi4F5 would result in a mixed oxidation state
for bismuth and 1 unpaired electron for the dication.
However, an ESR signal was not detected for the solid
sample, as well as a solution of 3 Æ C6Me6. The same
method was applied to assign F2 and F3. The sum of
two Bi–F(2), Bi–F(3) contacts is 0.71 and 0.67 v.u.,
while two Bi–O(2) and Bi–O(3) contacts would give
0.97 and 0.95 v.u., hence bridging atoms are most likely
fluorine. In addition, the fluorine NMR spectrum of the
freshly prepared SO2 solution of 3 Æ C6Me6 at ꢀ70 ꢁC
shows major 19F and 27Al NMR resonances of the
[Al(OC(CF3)3)4]ꢀ anion and a minor singlet resonance
at ꢀ220.5 ppm in the 19F NMR attributed to the fluo-
rine atoms in the [Bi4OF2Cl6]2+ cation.
Raman of 2, bands of [Al(OC(CF3)3)4]ꢀ anion (assignment see
[17,22b,22c]) are omitted for clarity
Observed band Literature data Assignment
108 (sh)
119 (s)
103 (sh)
119
m6(E00)[Bi5]3+
lattice mode, also observed
previously for anion and C6Me6
3þ
138 (sh)
336 (w)
380(w)
142 (sh)
343(w)
m1ðA01Þ½Bi5ꢁ
CH3 motion
378 (w)
CH3 motion perpendicular to the
plane of benzene skeleton
deformation mode of benzene
skeleton
450 (m)
450 (m)
554 (s)
553 (s)
breathing, benzene skeleton
m(C–CH3)
1294 (vs)
1373 (w)
1396 (m)
1418 (w)
1495 (m)
1581 (b, w)
2875 (sh)
2924 (b, vs)
1295 (m)
1364 (m)
1385 (m)
1438a
1462a
1583 (w)
2939 (vs)
2985 (vs)
dCH3 symmetry
dCH3 degenerate
dCH3 degenerate
dCH3 degenerate
m(C@C)
m(C–H)
m(C–H)
Assignment for [Bi5]2+ [4d,7b], C6Me6 [46].
a
Observed at low temperature in crystalline hexamethylbenzene
[46a].
Table 3
Observed IR bands of C6Me6 in 2, 3 Æ C6Me6, 4 and assignment [47]
2
3
4
C6Me6
Assignment
682
889
793
780
796
out of plane ring bending mode
1018
1062
1074
1022
1069
998
1057
in plane CH3 rocking
out of plane CH3 rocking
1061
1071
1102
1596
[C6Me6H]+a
a
Band at 1590 cmꢀ1 is one of the characteristic benzoid C@C skel-
etal stretching modes of the carbocation [48].
ically active and abstract oxygen and fluorine from the
nonafluorobutoxide ligand of the [Al(OC(CF3)3)4]ꢀ an-
ion and chlorine from the CH2Cl2 (see S.I. for a detailed
discussion). Abstraction of oxygen and fluorine from the
[Al(OC(CF3)3)4]ꢀ was observed previously by degrada-
tion of phosphorus iodine cations5 [27]. Bismuth alkox-
ides Bi(ORf)3 Rf = (C6H2(CF3)3) [28,29] decomposed
with C–F activation. C–Cl activation by electrophilic
metal centers followed by the chlorine transfer to the
metal have been observed for a wide range of metals
The dication contains four bismuth atoms at the apex
of an oxygen centered distorted tetrahedron, linked
across the edges by bridging halogen atoms (Figs. 2
and 3). The Bi1–F–Bi2 and Bi(1,2)–Cl–Bi(3,4) angles
in 3 are close to 90ꢁ within 2ꢁ and the Bi3–Cl–Bi4 angles
are 83.0(4)ꢁ and 85.0(4)ꢁ. Also, the estimated Bi4–Bi3
˚
distance is 3.602(1) A, shorter than the Bi1–Bi2 and
˚
Bi3–Bi4 contacts 3.93( 0.04) A. Each bismuth atom is
5
The proposed [27a,27b] decomposition mechanism of the salt of
capped by a weakly bound g6 C6Me6 ring7 [41,42]
[P2 I3 ]+ involved the formation of
a tight ion pair
[P2I3]+[Al(OC(CF3)3)4]ꢀ followed by liberation of [P2I3][OC(CF3)3]
and the very strong Lewis acid Al(OC(CF3)3)3 which abstract fluorine
from the [OC(CF3)3] and react with the [Al(OC(CF3)3)4]ꢀ forming
dimeric anion [(OC(CF3)3)3Al(l-F)Al(OC(CF3)3)3]ꢀ. The phosphorus
iodine cation abstract oxygen from the [OC(CF3)3] forming P2O3, P4,
C4F8. The final products of decomposition were [P2I3][(OC-
(CF3)3)3Al(l-F)Al(OC(CF3)3)3], phosphorus oxide, phosphorus alk-
oxide, P4 and fluorocarbon species.
6
Values used: Bi(+3)–F(ꢀ1) Ro = 1.99, B = 0.37, Bi(+3)–O(ꢀ2)
Ro = 2.094, B = 0.37, Bi(+3)–Cl(ꢀ1) Ro = 2.48, B = 0.37.
7
The separation distances between Bi(1) and C(301)–C(306) aro-
˚
˚
matic ring 2.69 A, Bi(2) and C(101)–C(106) aromatic ring 2.67 A, Bi(3)
and C(401)–C(406) aromatic ring 2.75 A, Bi(4) and C(201)–C(206)
aromatic ring 2.61 A.
˚
˚

2998
A. Decken et al. / Polyhedron 24 (2005) 2994–3003
We have estimated the lattice energy UPOT([Bi4OF2-
Cl6(C6Me6)4][Al(OC(CF3)3)4]2) as 912 kJ/mol8 [44]. This
is significantly larger than that of 1:1 salt with the same
anion, UPOT(Li[Al(OC(CF3)3)4]) 361 kJ/mol [19], but
smaller than the 1:2 salts UPOT(Ca[NO3]2) 2209 kJ/mol
and UPOT(MgI2) 1944 kJ/mol [18 (Table 2)]. Therefore,
the higher solubility of 3 Æ C6Me6 in SO2 compared with
the poor solubility of Ca(NO3)2 and MgI2 may arise
from the smaller lattice energy of 1:2 salts with the large
anion.
Cl2
F3
2.419(15)
0.31 v.u.
2.818(6)
0.40 v.u.
Bi1
2.395(13)
0.34 v.u.
2.818(6)
0.40 v.u.
2.330(12)
0.53 v.u.
The X-ray microanalysis confirms that 3 Æ C6Me6
contains Bi and Cl, as well as Al, F, C and O (S.I.).
The EI-MS shows ½C6Me6þꢁ and as well as fluorocarbon
cations derived from [Al(OC(CF3)3)4]ꢀ on decomposi-
tion of 3 Æ C6Me6. The IR spectrum of 3 Æ C6Me6
contains very strong absorption bands of the perfluori-
nated ligand of the anion. One Al–O band of the
[Al(OC(CF3)3)4]ꢀ anion was detected at 833 cmꢀ1 con-
sistent with an almost tetrahedral symmetry at the alu-
minium center. The observed absorption bands of the
C6Me6 in 3 Æ C6Me6 (Table 3) are shifted slightly higher
in energy, relative to the band for free C6Me6 [47], due
to coordination to the [Bi4OF2Cl6]2+ cation. For com-
parison, the Ln(III) complexes [LnCl2(C6Me6)][AlCl4]3
Ln = Nd, Sm, Gd, Yb exhibit the out of plane mode
at 770–780 cmꢀ1 and m(CH3) vibrations at 1010–
1030 cmꢀ1 [45], close to those of 3.
Cl1
O1
F2
Fig. 2. Environment of the Bi(1) atom in 3, neighbouring bismuth
atom and C6Me6 molecules are omitted for clarity.
Cl3
2.735(7)
2.657(7)
0.50 v.u.
Cl6
0.62 v.u.
Bi3
2.731(6)
0.51 v.u.
2.687(6)
0.57 v.u.
2.294(12)
0.58 v.u.
Cl1
3. Conclusions
Cl5
O1
Fig. 3. Environment of the Bi(3) atom in 3, neighbouring bismuth
atom and C6Me6 molecules are omitted for clarity.
Evidence is presented that we have prepared the SO2,
CH2Cl2 and C2H4Cl2 soluble salts [Bix][Al(OC(CF3)3)4]
(1) and [Bi5(C6Me6)4][Al(OC(CF3)3)4]3 (2), in a moderate
yields by the metathesis reaction between [Bi5][AsF6]3
and Li[Al(OC(CF3)3)4] in SO2 solution and in a solution
of CH2Cl2 that contained C6Me6. This implies that the
metathesis reaction in the presence of appropriate donor
ligand (arene) in SO2 and CH2Cl2 may generate several
of the related salts containing bismuth polyatomic cat-
ions. The UV–Vis of solutions of 1 in SO2 and 2 in
approximately perpendicular to the corresponding Bi–O
bond as illustrated in Fig. 1. The bismuth halogen dica-
tion core may be formally regarded as constructed from
one [BiF2]+ moiety, three [BiCl2]+ units, and [O]2ꢀ
which donates electron density to the four bismuth
atoms with the sum of the Bi–O valency units calculated
at 2.14(2) v.u.6 [40].
In VESPR terms [43], the first coordination around
Bi1 and Bi2 can be described as AX2X02YE (X = Cl,
X0 = F, Y = O, E = lone pair) and that of Bi3 and Bi4
as AX4YE illustrated for Bi1 and Bi3 in Figs. 2 and 3,
respectively, which include bond distances and valence
units. The corresponding figures for Bi2 and Bi4 are in-
cluded in the Supplemental materials. All the F–Bi–F,
F–Bi–Cl, Cl–Bi–Cl, O–Bi–F and O–Bi–Cl angles in 3
are in the range 72.3–76.4ꢁ. The sum of the valence units
around Bi3 is 2.78 v.u. (Bi1 is 1.98 v.u., Bi2 2.05 v.u., Bi4
2.66 v.u.), the remaining Bi valence units are derived
from the donation of electrons from the C6Me6 ring to
the positively charged bismuth in to the second coordi-
nation sphere of bismuth.
C2H4Cl2 were consistent with the presence of [Bi5]3+
[Bi8]2+, [Bi9]5+ and [Bi]+.
,
The bismuth homopolyatomic cations were shown to
be chemically reactive and the novel 1:2 salt [Bi4O-
F2Cl6(C6Me6)4][Al(OC(CF3)3)4]2 Æ C6Me6 containing the
bismuth cluster cation [Bi4OF2Cl6]2+ was isolated from
a solution of 2 in CH2Cl2. Formation of [Bi4OF2Cl6]2+
may be regarded as a self assembly of bismuth halide
and oxohalide moieties, however, it is difficult to assess
8
The volume of the C6Me6 (Vm = 0.252 nm3) [44] was subtracted
from the volume of 3 Æ C6Me6 (Vm = 3.402 nm3), obtained from
crystallographic data in order to provide the volume of
3
(Vm = 3.150 nm3). The obtained volume was used for calculation of
UPOT(3) using Eq. (3) [18] and parameters a = 133.5, b = 60.9.

A. Decken et al. / Polyhedron 24 (2005) 2994–3003
2999
Table 4
the features that governed the [Bi4OF2Cl6] stoichiometry
Crystallographic data of the X-ray diffraction studies of 3 Æ C6Me6
by decomposition of the bismuth homopolyatomic cat-
ions under the prevailing experimental conditions. We
propose that the process involved fluorine and oxygen
transfer from the nonafluorobutoxide ligand and chlo-
rine transfer from the CH2Cl2 and conclude that the
bulky anion facilitates the formation of a discrete oxy-
gen-centered fluorine- and chlorine-bridged bismuth
cluster in a complex with hexamethylbenzene.
3 Æ C6Me6
Formula
Molecular formula
C92H90Al2Bi4Cl6F75O8
[Bi4OF2Cl6(C6Me6)4]
[Al(OC(CF3)3)4]2 Æ C6Me
3848.22
Mr
Temperature (K)
Radiation used (k [A])
Crystal description
Crystal size (mm)
Crystal system
198(1)
˚
Mo Ka (0.71073)
orange, needle
0.1 · 0.1 · 0.5
orthorhombic
P212121
15.8671(10)
25.8211(18)
33.209(2)
Space group
4. Experimental
˚
a (A)
˚
b (A)
˚
4.1. General remarks
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
V (A )
Z
90
90
90
All operations were performed using standard
Schlenk line techniques under a purified nitrogen atmo-
sphere. Solid reagents and crystals were manipulated in
a Vacuum Atmospheres Dri-Lab equipped with a Dri-
3
˚
13605.8(16)
4
7360
1.879
5.437
F(000)
qcalc (g cmꢀ3
)
˚
Train (HE-493) and 1 kg of 3 A molecular sieves con-
l (mmꢀ1
)
tained in an internal circulating drying unit. Reactions
in SO2 were carried out in a jointless, single apparatus
fitted with Teflon in glass Rotoflo valves (HP 6K) and
consisting of two thick walled bulbs (V = 50 ml) linked
by a glass tube incorporating a sintered fine-porosity
glass frit. The compounds [Bi5][AsF6]3 Æ SO2 and Li[Al-
(OC(CF3)3)4] were prepared by the literature methods
[23a,4d] and the identity of [Bi5][AsF6]3 Æ SO2 was sup-
ported by IR. The IR spectrum of Li[Al(OC(CF3)3)4] in-
cluded in the S.I. has not been previously reported.
Sulfur dioxide was dried over P2O5 and distilled prior
to use. CH2Cl2 and CDCl3 were dried over CaH2 and
degassed. NMR spectra were recorded using Varian
400 NMR spectrometer. Proton and 13C chemical shifts
are reported in d units downfield from Me4Si with the
solvent as the reference signal. CClF3 was used as a ref-
erence for 19F spectra and aqueous solutions of AlCl3
Total reflections
Unique reflections
Rint
94818
30455
0.1001
1.2–27.50
Scan range H (ꢁ)
Completeness to Hmax (%)
Index ranges
99.2
ꢀ20 6 h 6 20; ꢀ32 6 k 6 33;
ꢀ42 6 l 6 39
30455/125/712
0.0858, 0.2289
0.2036, 0.2622
1.009
Data/restrains/parameters
R1, wR2 [I > 2r(I)]
R1, wR2 (all data)
Goodness-of-fit on F2
Maximum/minimum
electron density (e A
Minimum/maximum
transmission ratio
3.016 and ꢀ1.425
ꢀ3
˚
)
0.860
P
P
P
P
wR2 ¼ ð ½wðF 2o ꢀ F 2c Þ ꢁ= ½F o4ꢁÞ1=2, R1 ¼ kF oj ꢀ jF ck= jF oj, weight ¼
2
2
1=½r2ðF 2oÞ þ ð0:0745 ꢄ PÞ ꢁ; where P ¼ ðmaxðF o2 ;0Þ þ 2 ꢄ F 2c Þ=3.
7
and Li[ClO4] were used as a references in 27Al and Li
NMR spectra, respectively. NMR samples were pre-
pared in 10 and 5 mm thick walled NMR tubes fitted
with J. Young valves. Mass spectra were recorded using
a KRATOS ms 50 TC mass spectrometer equipped with
the EI source, 30 ev. by the direct inlet method from
samples sealed in dried glass m.p.t. tubes. FT-IR spectra
(resolution 1 cmꢀ1, 128 scans) were recorded using a
Thermo Nicolet spectrometer (Nexus 470 FT-IR). FT-
Raman spectra were obtained from neat samples, sealed
under nitrogen atmosphere in glass capillaries, using
Bruker RFS 100 FT-Raman spectrometer incorporating
a Nd:YAG laser (emission wavelength: 1.06 lm; maxi-
mum output laser power: 80 mW), 1000 scans, resolu-
tion 4 cmꢀ1. We attempted to record FT-Raman
spectra of all species; however, the coloured samples 1
and 3 showed fluorescence, compound 2 gave a Raman
spectrum with a low signal-to-noise ratio. The UV–Vis
spectrum of 1 in SO2 was measured using HP-8452A
diode array spectrophotometer, at room temperature,
300–820 nm range, 14 mg of solid containing 90% 1
and 10% Li[Al(OC(CF3)3)4] in (6 g, 4.11 ml) of SO2
0.1 cm cell. The compound 2 were measured using a
Cary 5E UV–Vis–NIR spectrometer, at room tempera-
ture, in 0.2 cm cells. Two spectra, one containing data
collected from 3000 to 400 nm and one from 800 to
300 nm were measured using 23.5 mg of sample 2 and
3.8636 g of C2H4Cl2. Melting points were measured in
sealed capillary tubes under nitrogen and are not cor-
rected. X-ray microanalysis was performed with a JEOL
JSM-6400 SEM, equipped with an Edax Genesis X-ray
micro analyser. Operating conditions: vacuum close to
10ꢀ6 Torr, accelerating voltage 15 kV, probe current
1.5 nA, spectra collection time 60 s. Samples were
coated with carbon, using an Edwards vacuum evapora-
tor. Elemental analysis was carried out by Galbraith
Laboratories, Inc.

3000
A. Decken et al. / Polyhedron 24 (2005) 2994–3003
4.2. Preparation of salts 1
at ꢀ24 ꢁC for 2 days. The dark brown (almost black)
crystals that formed were separated by filtration. The
next crop of the crystalline dark brown solid was ob-
tained from the supernatant solution by crystallization
at ꢀ24 ꢁC for 2 days. Yield of [Bi5(C6Me6)4][Al(OC-
(CF3)3)4]3 (1.64 g, 55% based the Li[Al(OC(CF3)3)4]).
C96H72F108O12Al3Bi5: Calc. C, 25.07; H, 1.56; F,
44.66; Al, 1.76; Bi, 22.74. Found: C, 24.84; H, 2.01; F,
43.80; Al, 1.26; Bi, 23.91%. 184–186 ꢁC decomposition.
EI-MS (30 eV, heating r.t. ꢀ170 ꢁC): m/z (%) = 197 (5)
A dried two bulbed (50 ml) vessel equipped with Tef-
lon in glass with Rotoflo valves (HP 6K), was charged
with the Li[Al(OC(CF3)3)4] (0.8 g, 0.8 mmol) and
[Bi5][AsF6]3 Æ SO2 (2.7 g, 1.6 mmol). SO2 (15 ml) was
condensed onto the mixture of reagents at ꢀ196 ꢁC.
The resulting mixture was rigorously stirred at r.t. for
5 days. A dark brown solution was filtered from 2.6 g
of yellow insoluble solid and SO2 was removed under
dynamic vacuum to give a brown solid. Yield: 0.9 g,
70% based on the Eq. (1). The relative amount of Li[A-
l(OC(CF3)3)4] in the reaction product was established as
[L+ ꢀ 2F], 167 (17) [L+ ꢀ CF3], 162 (100) ½C6Me þꢁ,
6
147 (12) [L+ ꢀ CF4], 97 (15) [L+ ꢀ C2F3O], L =
OC(CF3)3. A non-volatile solid residue remained. 27Al
NMR (104.2 MHz, SO2, r.t.); dAl (ppm) = 31.6. 19F
NMR (376.3 MHz, SO2, r.t.), dF (ppm) = ꢀ75.9 (s);
13C NMR (100.6 MHz, SO2, r.t.), dC (ppm) = 16.5
(C6Me6), 121.7 (q, C(CF3)3, J = 291 Hz), 134.3
7
10% by measuring the intensity of the Li NMR reso-
nance relative to that in the spectrum of a solution of
Li[Al(OC(CF3)3)4] in SO2 at a known concentration. 1
could be a mixture of individual compounds. Result of
elemental analysis could be interpreted based on the
model 90% of [Bi5(SO2)3][Al(OC(CF3)3)4]3 and 10% of
Li[Al(OC(CF3)3)4] or alternatively [Bi4.33][Al(OC-
(CF3)3)4]3 and 10% of Li[Al(OC(CF3)3)4]: Calc. C,
14.49; Bi, 22.73; F, 51.65. Found: C, 14.24; Bi, 21.41;
F, 51.73%. EI-MS (30 eV, heating r.t. ꢀ170 ꢁC): m/z
(%) = 706 (1) [An+–C3F11O], 691 (1) [An+–C(CF3)3–
3F], 504 (30) [An+–C(CF3)3–3CF3–2F], 489 (10)
[An+–L–C3F10O], 371 (2) [An+–2L–CF3–3F], 302 (4)
[An+–2L–2CF3–3F], 287 (12) [An+–2C(CF3)3–3CF3–2F],
64 (25) ½SO2þꢁ, An = [Al(OC(CF3)3)4], L = OC(CF3)3,
non-volatile solid residue left, calculated theoretical
isotopes distribution matched that experimentally
observed for all peaks. 27Al NMR (104.2 MHz, SO2,
r.t.), dAl (ppm) = 32.5 (s, [Al(OC-(CF3)3)4]ꢀ). 19F NMR
(376.3 MHz, SO2, r.t.), dF (ppm) = ꢀ72.4; ꢀ74.1 decom-
position products of [Al(OC(CF3)3)4]ꢀ, ꢀ74.9 (s, [Al-
(OC(CF3)3)4]ꢀ); IR (KBr, cmꢀ1, Nujol): 1377 (s), 1364
(m), 1355 (s), 1299 (s), 1273 (s), 1247 (s), 1215 (s), 1173
(s), 1120 (m), 972 (vs), 892 (w), 864 (w), 841 (m), 832
(m), 798 (m), 781 (w), 770 (w), 760 (w), 755 (w), 744
(w), 726 (vs), 620 (w), 580 (m), 571 (m), 561 (m), 550
(w), 537 (s), 480 (m), 450 (m), 397 (w).
1
(C6Me6); H NMR (400 MHz, SO2, r.t.), dH (ppm) =
5.2 (s), 4.7 (s), 3.3 (s), 3.1(s), 2.8 (s), 2.6 (s, C6Me6 in
complex, major signal, relative intensity 85%), 2.5 (s),
2.1 (s), 2.0 (s). The 5.2–2.7 and 2.1–2.0 ppm minor reso-
nances are assigned to the products of oxidation of
C6Me6, see Supplemental materials, relative intensity is
measured relative to all resonances in spectrum; IR of
2 (KBr, cmꢀ1, Nujol): 1301 (vs), 1276 (vs), 1241 (vs),
1216 (vs), 1165 (s), 1135 (m), 1074 (w, C6Me6, Table 5),
1062 (w, C6Me6), 1018 (vw, C6Me6), 973 (vs), 832 (m,
Al–O), 793 (w, C6Me6), 755 (w), 728 (vs), 571 (w), 561
(m), 537 (m), 447 (m).
Note: keeping the supernatant solution longer than
5 days at ꢀ24 ꢁC lead to formation of yellow crystals
3, 4 and a grey powder Bi (X-ray elemental micro-
analysis).
4.4. Isolation of [Bi4OF2Cl6(C6Me6)4]-
[Al(OC(CF3)3)4]2 Æ C6Me6 3 Æ C6Me6: and
[C6Me6H][Al(OC(CF3)3)4] (4)
A mixture of Li[Al(OC(CF3)3)4] (1.5 g, 1.5 mmol),
[Bi5][AsF6]3 (0.86 g, 0.5 mmol) and C6Me6 (0.4 g,
2.5 mmol) in CH2Cl2 (40 ml) was stirred for 4 h in a
100 ml Schlenk flask. The dark brown solution was
filtered and concentrated to approximately 10 ml and
left at ꢀ24 ꢁC for 2 weeks. Yellow crystals, a red-brown
solid and a grey powder (Bi, X-ray elemental microanal-
ysis) deposited. The solution was filtered and concen-
trated to 2–3 ml and held at ꢀ24 ꢁC for 3 weeks.
Orange crystals (yellow as a powder) formed and were
separated manually (0.45 g) from the reaction products.
The resulting crystals were a mixture of 3 Æ C6Me6, 4
(yellow)3 and colourless crystals,4 the presence of the
[C6Me6H]+ cation was confirmed by IR. Result of
elemental analysis was interpreted based on the model
75% of 3 Æ C6Me6 and 25% of 4: Calc. C, 28.93; H,
2.17; F, 42.88. Found: C, 30.31; H, 2.16; F, 42.89%.
Note: The metathesis reaction between the poorly
SO2 soluble [Bi5][AsF6]3 and 2,3 equivalents of highly
soluble Li[Al(OC(CF3)3)4] in SO2 followed by removal
of the insoluble products afforded a mixture of [Bix][Al-
(OC(CF3)3)4] and Li[Al(OC(CF3)3)4] (IR, 7Li NMR,
EI-MS), with the Li[Al(OC(CF3)3)4] as the major
product.
4.3. Preparation of [Bi5(C6Me6)4][Al(OC(CF3)3)4]3
(2)
A mixture of Li[Al(OC(CF3)3)4] (1.87 g, 1.9 mmol),
[Bi5][AsF6]3 (3.1 g, 1.9 mmol) and C6Me6 (0.6 g,
3.8 mmol) in a 100 ml Schlenk flask was stirred in
CH2Cl2 (40 ml) for 4 h. The dark brown solution was fil-
tered and concentrated to approximately 4 ml and held

A. Decken et al. / Polyhedron 24 (2005) 2994–3003
3001
Compound [Bi4OF2Cl6(C6Me6)4][Al(OC(CF3 )3)4]2 Æ
C6Me6 3 Æ C6Me6: EI-MS (30 eV, heating r.t. ꢀ170 ꢁC):
m/z (%) = 679 (4) [An+–C(CF3)3–CF3], 477 (20) [An+–
L–C(CF3)3–2F], 461 (10) [An+–2L–2F], 447 (2), [An+–
2C(CF3)3–C2F4], 443 (10) [An+–L–C(CF3)3–CF3], 162
(100) ½C6Me6þꢁ, non-volatile black solid residue
remained; 19F NMR (376.3 MHz, CDCl3, r.t.), dF
(ppm) = ꢀ74.1 (s), ꢀ75.3 (s); 1H NMR (400 MHz,
CDCl3, r.t.), dH (ppm) = 3.8 (s), 2.3 (s). The compound
was very poorly soluble in CDCl3, initially dissolved in
SO2 followed by the deposition of a solid over 10–
30 min. NMR spectra were measured for the freshly pre-
pared clear SO2 solution at low temperature. 19F NMR
(376.3 MHz, SO2, ꢀ70 ꢁC), dF (ppm) = ꢀ73.9 (s), ꢀ75.0
tals were coated with Paratone-N oil, mounted using a
glass fibre and frozen in the cold nitrogen stream of
the goniometer. A hemisphere of data was collected on
a Bruker AXS P4/SMART 1000 diffractometer using
x and h scans with a scan width of 0.3ꢁ and 30 s expo-
sure times. The detector distance was 5 cm. The data
were reduced (SAINT) [49] and corrected for absorption
(SADABS) [50]. The structure was solved by direct meth-
ods and refined by full-matrix least squares on F2 (SHEL-
XTL) [51] (Table 4). The compound was a racemic
mixture. Anisotropic refinement was employed for all
Bi, Cl and Al atoms and F2–F3, O1–O9 and C1–C8.
All other atoms were refined isotropically. Hydrogen
atoms were included in calculated positions and refined
using a riding model. Hexamethylbenzene molecules
were restraint to equal distances within the ring and be-
tween the methyl groups. CF3 groups were refined as
1
(s), ꢀ75.5 (s), ꢀ195.1 (s, Al–F), ꢀ220.6 (s, Bi–F); H
NMR (400 MHz, SO2, ꢀ70 ꢁC), dH (ppm) = 7.4 (Dx1/2
91 Hz), 4.9 (Dx1/2 13 Hz, 2H, C6Me5H2OC(CF3)3),
4.56 (s, Dx1/2 1.3 Hz, 2H, (C6Me6)2CH2), 3.20 (Dx1/2
3 Hz, weak), 3.13 (Dx1/2 3 Hz, 3H, C6Me5-
CH2OC(CF3)3), 3.05 (Dx1/2 3 Hz, 3H, (C6Me6)2CH2),
2.95 (Dx1/2 3 Hz, 6H, C6Me5CH2OC(CF3)3), 2.86
(Dx1/2 3 Hz, 6H, (C6Me6)2CH2), 2.64 (Dx1/2 3 Hz, 6H,
C6Me5CH2OC(CF3)3), 2.58 (Dx1/2 3 Hz, 6H, (C6Me6)2-
CH2), 2.40 (Dx1/2 9 Hz), 1.85 (Dx1/2 3 Hz, weak), 1.76
(Dx1/2 3 Hz C6Me6 or [C6Me6H]+), 0.47–0.35 (aliphatic
protons). 27Al NMR (104.2 MHz, CH2Cl2, r.t.); dAl
(ppm) = 31.6 (s). IR (KBr, cmꢀ1, Nujol): 1593 (w),
1300 (vs), 1277 (vs), 1251 (vs), 1240 (vs), 1218 (vs),
1165 (s), 1102 (w, C6Me6), 1069 (w, C6Me6), 1022 (w,
C6Me6), 973 (vs), 831 (m), 780 (sh, C6Me6), 728 (w),
623 (w, Al–F*), 610 (w, Al–F*), 569 (w), 560 (m), 537
(m), 447 (m), * impurity of aluminium fluoride com-
plexes resulted by degradation of [Al(OC(CF3)3)4]ꢀ.
Compound [C6Me6H][Al(OC(CF3)3)4] (4): EI-MS
(30 eV, heating r.t. ꢀ170 ꢁC): m/z (%) = 850 (5)
[An+–C2F4O], 675 (8) [An+–L–3F], 536 (1) [An+–L–
2CF3–3F], 478 (10) [An+–2L–F], 477 (20) [An+–L–
C(CF3)3–2F], 461 (10) [An+–2L–2F], 447 (2),
[An+–2C(CF3)3–C2F4], 445 (10) [An+–L–C(CF3)3–
CF3], 443 (10) [An+–L–C(CF3)3–CF3], 441 (10)
˚
regular tetrahedra with fixed bond distances of 1.32 A.
The isotropic thermal parameter for C72 was fixed.
Refinement was non-convergent and anisotropic refine-
ment lead to many non-positive definites.
Acknowledgement
Acknowledgement is made to NSERC (Canada) and
PRF(Canada) for financial support and Neil Buford,
Heather Phillips (Dallhouse University) for attempts to
measure FT-Raman spectra, Dr. Dr. Kathryn E. Preuss,
for measuring of UV–Vis spectra in dichloroethane.
Appendix A. Supplementary data
Crystallographic data (excluding structure factors) for
the structures in this paper have been deposited with the
Cambridge Crystallographic Data Center as Supplemen-
tary Publication No. CCDC 250743. Copies of the data
can be obtained, free of charge, on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +44
1223 336033; e-mail: deposit@ccdc.cam.ac.ukor http://
www.ccdc.cam.ac.uk). X-ray microanalysis of reaction
products, NMR Reactions in situ and NMR investigation
of oxidation of C6Me6, IR spectrum of Li[Al(OC(CF3)3)4]
350–4000 cmꢀ1, UV–Vis spectra 300–800 and 400–
1100 cmꢀ1, structure 3 Æ C6Me6, details of discussion. Sup-
plementary data associated with this article can be found,
in the online version, at doi:10.1016/j.poly.2005.06.032.
[An+–2L–3F], 162 (100) ½C6Me þꢁ; NMR spectra of
6
4 are similar to that of 3 since the yellow crystals
are a mixture of both compounds. IR (KBr, cmꢀ1
,
Nujol): 3300 (br), 1596 (m, [C6Me6H]+), 1301 (vs),
1276 (vs), 1251 (vs), 1240 (vs), 1217 (vs), 1165 (s),
1071 (w, [C6Me6H]+), 1061 (w, [C6Me6H]+), 973
(vs), 889 (w, [C6Me6H]+), 831 (m), 756 (w), 728 (w),
682 (w, [C6Me6H]+), 571 (w), 560 (w), 537 (w), 447
(m). Absorption band at 1590 cmꢀ1 is one of the char-
acteristic benzoid C@C skeletal stretching modes of
the carbocations [48].
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