FULL PAPER

DOI: 10.1002/chem.201102960

Halogenated Benzene Cation Radicals

Matthias J. Molski,[a] Doreen Mollenhauer,[a] Sebastian Gohr,[a] Beate Paulus,[a]

Monther A. Khanfar,[b] Hashem Shorafa,[a] Steven H. Strauss,[c] and Konrad Seppelt*[a]

Abstract: The halogenated benzenes
C6HF5, 2,4,6-C6H3F3, 2,3,5,6-C6H2F4,
C6F6, C6Cl6, C6Br6, and C6I6 were con-
verted into their corresponding cation
radicals by using various strong oxi-
dants. The cation-radical salts were iso-
lated and characterized by electron
paramagnetic resonance (EPR) spec-
troscopy and by single-crystal X-ray
diffraction. The thermal stability of the
cation radicals increased with decreas-
ing hydrogen content. As expected, the
cation radicals [C6HF5]+ and 2,3,5,6-
[C6H2F4]+ had structures with the same
geometry as C6HF5 and 2,3,5,6-
[C6H2F4]. In contrast, the cation radi-
cals [C6F6]+, [C6Cl6]+, and possibly also
[C6Br6]+ exhibited Jahn–Teller-distort-
ed geometries in the crystalline state.
Keywords: benzene · cations · crys-
tal structures · Jahn–Teller distor-
tion · X-ray diffraction
In the case of C6F6+Sb2F11 , two low-
symmetry geometries were observed in
the same crystal. Interestingly, the
structures of the cation radicals 2,4,6-
[C6H3F3]+ and C6I6+ did not exhibit
Jahn–Teller distortions. DFT calcula-
tions showed that the explanation for
the lack of distortion of these cations
from the D3h or D6h symmetry of the
neutral benzene precursor was differ-
ent for 2,4,6-[C6H3F3]+ than for [C6I6]+.

Introduction zenes, see the Supporting Information, Table SI-1). By anal-

Benzene, C6H6, is one of the archetypal organic molecules
owing to its D6h symmetry, aromaticity, ring current, and sta-
bility. Because its exceptional stability is related to the de-
localization of six p electrons, it is expected that variation of
the electron count, such as in [C6H6]+, [C6H6]2+, and
[C6H6] , would result in highly reactive species. Herein, we
focused on the cation radicals C6X6+, with X = F, Cl, Br, and
I (hereafter, to avoid confusion, the generic term “benzene”
is used to refer to C6H6 and all of its possible monocyclic de-
rivatives, the formula “C6H6” is used to refer specifically to
the parent molecule). In the gas phase, C6H6 has a first ioni-
zation potential (IP) of 9.25(2) eV,[1] and the substitution of
hydrogen by halogen atoms causes this to increase in a sys-
tematic manner[1–3] (for a list of IP values for relevant ben-
[a] M. J. Molski, D. Mollenhauer, S. Gohr, Prof. Dr. B. Paulus,
Dr. H. Shorafa, Prof. Dr. K. Seppelt
Freie Universitt Berlin
Institut fr Chemie und Biochemie
Fabeckstrasse 34-36, 14195 Berlin (Germany)
Fax: (+ 49) 30-838-54289
E-mail: seppelt@zedat.fu-berlin.de
[b] Prof. M. A. Khanfar
Chemistry Department, The University of Jordan
Amman (Jordan)
[c] Prof. S. H. Strauss
Department of Chemistry, Colorado State University
Fort Collins, CO 80523 (USA)
Supporting information for this article, including additional informa-
tion on selected structures, calculated orbital energies, and EPR spec-
tra, is available on the WWW under http://dx.doi.org/10.1002/
chem.201102960.
ogy to other high-IP molecules, such as O2 (12.07 eV), Cl2
(11.51 eV), Br2 (10.51 eV), and I2 (9.22 eV), all of which
have been successfully oxidized to produce cation radicals
that were isolable without further reaction (i.e., [O2]+,[4]
[Cl4]+,[5] [Br2]+,[6] and [I2]+,[7] respectively), we reasoned that
some benzene cation radicals should be obtainable.
The cation radical [C6H6]+ has been observed spectroscop-
ically in the gas phase.[8, 9] However, in a condensed phase, it
may be the most-difficult benzene cation radical to study.
Although C6H6 has a lower IP than the other benzenes stud-
ied herein, side-reactions following oxidation, such as the
loss of a proton, may be very rapid and therefore unavoida-
ble. Nevertheless, EPR spectra have been observed. The ox-
idation of benzene by persulfate in concentrated sulfuric
acid gave a poorly resolved seven-line spectrum, and a reac-
tion mixture containing C6H6 and NbF5 has been interpreted
as that of the ion-pair [C6H6+Nb2F11 ].[10] On the other hand,
C6F6, with an IP of 9.88(5) eV,[1] should be the most-difficult
benzene to oxidize, but, once obtained, its cation radical
might be more stable than all other benzene cation radicals.
As we will show below, the stability of [C6H6-nFn]+ cation
radicals increases as the value of n increases.
In addition to demonstrating that benzene cation radicals
can be isolated in a condensed phase, the central focus of
this work was the determination of their structures. For neu-
tral precursors with D6h and D3h symmetry, Jahn–Teller dis-
tortions are expected following oxidation into the cation
radicals. But what particular lower-symmetry structure
should be present for a given cation radical in a given con-
densed-phase environment is an open question. It has been
shown theoretically that gas-phase [C6H6]+, [C6F6]+, and
2,4,6-[C6H3F3]+ should distort into D2h ([C6H6]+, [C6F6]+) or

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C2v structures (2,4,6-[C6H3F3]+).[11–21] However, in each case,
two alternative structures were predicted that were very
close in energy: a quinoid structure and a bis-allyl-like struc-
ture (hereinafter referred to as the bis-allyl structure or ge-
ometry). The quinoid cations were predicted to have two
short C C bonds and four longer ones, whereas the bis-allyl
cations were predicted to have four short and two longer C
C bonds.
All benzene cation radicals can be unstable at room tem-
perature and hence susceptible to secondary reactions.
Therefore, our plan was to first detect these species qualita-
tively by their often intense color, then to study them in so-
lution by EPR spectroscopy, and finally to isolate them as
their crystalline salts and determine their structures by X-
ray diffraction. The latter part of the plan was deemed nec-
essary because the Jahn–Teller distortion of benzene cation
radicals, which were made from a D6h-symmetry- or D3h-
symmetry-neutral benzene precursor, should not be observa-
ble in isotropic EPR spectra owing to the rapid interconver-
sion of equivalent Jahn–Teller-distorted isomers in solution.
However, the observation of Jahn–Teller distortions by crys-
tallography could be hampered by positional disorder of the
pseudo-hexagonal cations. In an attempt to avoid this prob-
lem, special emphasis was placed on growing single crystals
very slowly at low temperatures.
Results
EPR g values and hyperfine coupling constants (aF and aH)
for solutions of [C6HF5]+ACHTUNGRE[AsF6] and 2,3,5,6-[C6H2F4]+-
ACHTUNGRE[SbF6] in SO2, [C6F6]+ACHTUNGRE[Sb2F11] and [C6Cl6]+ACHTUNGRE[Sb2F11] in
SO2ClF, and microcrystalline [C6I6]+ACHTUNGRE[AsF6] and [C6I6]+-
ACHTUNGRE[SbF6] are listed in Table 1. The EPR spectra of [C6F6]+-
ACHTUNGRE[Sb2F11] , [C6HF5]+, and [C6H2F4]+ are shown in the Sup-
porting Information, and matched those reported in the lit-
erature.[22]
Table 1. EPR spectroscopic parameters.[a]
Compound Solvent T g
[8C]
ACHTUNGRE[C6F6]+ACHTUNGRE[Sb2F11] [b] SO2ClF 20 2.0022
ACHTUNGRE[C6HF5]+ACHTUNGRE[AsF6] [c] SO2 70 2.004
2,3,5,6-[C6H2F4]+- SO2 70 2.004
ACHTUNGRE[SbF6] [d]
ACHTUNGRE[C6Cl6]+ACHTUNGRE[Sb2F11] SO2ClF 25 2.010
ACHTUNGRE[C6I6]+ACHTUNGRE[AsF6] , none 25,
ACHTUNGRE[C6I6]+ACHTUNGRE[SbF6] (solid) 70,
196
[a] All data are from this work unless otherwise noted. [b] Data taken
from reference [26]. [c] Literature values from reference [22]: g = 2.0036,
aF(1,5)–aF(2,4) = 25.8ACHTUNGRE(0.2) G, aF(3) = (4.8  0.2) G. [d] Literature values from
reference [22]: g = 2.0039, aF = (25.8  0.3) G.
Selected crystal data and structure-refinement parameters
for the X-ray structures reported herein are listed in
Table 2. Figures 1–6 show the structures of most of the ben-
zene cation radicals and, only where relevant, details of
cation–anion interactions.
DFT-predicted relative energies for three limiting geome-
tries for the isolated [C6X6]+ cation radicals are listed in
Table 3 (X = F, Cl, Br, I). DFT-predicted C C bond lengths
were compared with their corresponding lengths as deter-
mined by X-ray crystallography for neutral molecules C6X6
and for the [C6X6]+ cation radicals in Table 4. Similar com-
parisons were made between the [C6HF5]+, 2,4,6-[C6H3F3]+,
and 2,3,5,6-[C6H2F4]+ cation radicals in Table 5, which also
includes the DFT-predicted C C bond lengths for the
2,4,5,6- and 3,4,5,6-[C6H2F4]+ cation radicals.
Discussion
ACHTUNGRE[C6F6]+: This cation radical may have been first observed by
EPR spectroscopy in a mixture of C6F6 and SbF5, which ex-
hibited hyperfine splittings that were attributable to six
equivalent F atoms.[22] Later, the yellow compound [C6F6]+-
ACHTUNGRE[AsF6] was obtained by oxidizing C6F6 with [O2]+ACHTUNGRE[AsF6] ,
but information about the structure of the cation radical
could not be obtained.[23, 24] It has also been reported that
CrF5 can oxidize C6F6 into [C6F6]+.[25]
In 2009, we reported that OsF6/SbF5 or [O2]+ACHTUNGRE[Sb2F11] oxi-
dized C6F6 into [C6F6]+ in anhydrous HF solution. Our EPR
spectrum,[26] the parameters of which are listed in Table 1,
was identical to the previously published spectrum.[22] Two
salts, [C6F6]+ACHTUNGRE[Os2F11] and [C6F6]+ACHTUNGRE[Sb2F11] , were isolated
and structurally characterized (they were found to be iso-
structural).[26] The X-ray structures revealed two pleasant
surprises: 1) the two independent, Jahn–Teller-distorted
[C6F6]+ cation radicals in the asymmetric unit were not dis-
ordered, and 2) they had different distorted geometries
(Figure 1). In addition, both structures were determined
very precisely. The R1 value and the standard error for indi-
vidual C C bond lengths for [C6F6]+ACHTUNGRE[Sb2F11] were 0.015 and
either 0.3 or 0.4 pm, respectively. The two “bond-stretch iso-
mers”[27] discovered in the same unit cell were indeed the
Hyperfine coupling
constants [G]
quinoid and bis-allyl isomers predicted by DFT and ab initio
calculations.[21, 26]
aF = 13.65
aF(1,5)–aF(2,4) = 26.9 The isomeric [C6F6]+ cations were in distinctly different
aF(3) = 4.8, lattice environments, and that electrostatic cation···anion in-
aH = 1.4 teractions caused the relative stabilization of one geometry
aF = 25.6, or the other. In our analysis, only C F atomic distances
aH = 1.0
shorter than about 326 pm were considered because the van
broad envelope
very broad signal der Waals radii of F and C atoms are 147–150 and 176–
177 pm, respectively. The bis-allyl structure, with four short
and two longer C C bonds, should have more positive
charge localized on the C2 and C3 atoms than on the C1
and C4 atoms. In harmony with this prediction, the closest
C1···F and C4···F contacts were 325.5(3) ( 2) and
318.2(3) pm ( 2), respectively, whilst the closest C2···F con-
tacts were 272.4(3) and 275.7(3) pm, respectively, and the
closest C3···F contacts were 272.2(3) and 281.9(3) pm, re-
spectively, about 50 pm shorter. The situation for the qui-

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Halogenated Benzene Cation Radicals
FULL PAPER
Table 2. Crystal data and structure-refinement parameters.
Compound ACHTUNGRE[C6HF5]+ACHTUNGRE[AsF6] ACHTUNGRE[C6H2F4]+ACHTUNGRE[SbF6] ·2 HF ACHTUNGRE[C6H3F3]+ACHTUNGRE[AsF6] ACHTUNGRE[C6H3F3]+ACHTUNGRE[SbF6 ] ACHTUNGRE[C6Cl6]+ACHTUNGRE[Sb2F11]
formula C6HF11As C12F21H5Sb2 C6F9H3As C6F9H3Sb C6Cl6F11Sb2
Mr 356.99 791.66 321.00 367.83 737.27
crystal system monoclinic triclinic hexagonal hexagonal monoclinic
space group P21/n P1̄ R3̄ R3̄c P21/m
a [pm] 790.74(8) 805.3(2) 973.6(1) 991.66(7) 789.9(2)
b [pm] 2054.7(2) 1020.2(3) 973.6(1) 991.66(7) 1530.2(2)
c [pm] 1170.91(1) 1273.3(4) 1579.3(2) 1605.5(2) 830.3(2)
a [8] 90 99.33(1) 90 90 90
ß [8] 100.461(3) 98.28(1) 90 90 116.80(1)
g [8] 90 93.27(1) 120 120 90
V,  106 [pm3] 1870.9(3) 1018.0(5) 1296.5(3) 1367.3(2) 895.9(3)
Z 8 2 6 6 2
1calcd [Mg m 3] 2.535 2.583 2.467 2.680 2.733
m [mm 1] 3.787 2.841 4.051 3.139 4.006
crystal size [mm] 0.3  0.1  0.1 0.15  0.14  0.05 0.5  0.01  0.01 0.2  0.05  0.05 0.4  0.2  0.01
color yellow green red red brown blue
independent data 3290 10086 443 468 2752
Rint 0.045 0.0251 0.0230 0.0181 0.0277
parameters 336 336 29 30 115
R1, wR2 0.0328, 0.0901 0.026, 0.0543 0.0188, 0.0477 0.0111, 0.0304 0.0237, 0.0513
ACHTUNGRE[C6I6]+ACHTUNGRE[AsF6] ACHTUNGRE[C6I6]+ACHTUNGRE[SbF6] ACHTUNGRE[C6I6]+[HACHTUNGRE(SO3CF3)2] 2,3,5,6-C6H2F4
formula C6F6I6As C6F6I6Sb C8F6HI6O6S2 C6F4H2
Mr 1022.38 1069.21 1132.61 150.08
crystal system monoclinic monoclinic triclinic monoclinic
space group C2/c C2/c P1̄ P21/c
a [pm] 1820.2(14) 1838.9(2) 945.2(7) 448.0(1)
b [pm] 669.6(6) 673.54(7) 986.2(5) 1025.1(2)
c [pm] 1456.2(13) 1484.2(2) 1274.2(9) 630.1(2)
a [8] 90 90 75.39(2) 90
ß [8] 109.36(2) 109.243(5) 89.76(2) 107.99(3)
g [8] 90 90 81.92(3) 90
V,  106 [pm3] 1674(3) 1735.5(3) 1137.3(13) 275.3(1)
Z 4 4 2 2
1calcd [Mg m 3] 4.056 4.092 3.307 1.811
m [mm 1] 13.133 12.303 8.448 0.201
crystal size [mm] 0.15  0.04  0.01 0.3  0.05  0.01 0.3  0.05  0.01 0.2  0.2  0.2
color black black black colorless
independent data 2559 2627 4935 1948
Rint 0.0291 0.0283 0.0387 0.0177
parameters 87 87 256 50
R1, wR2 0.0248, 0.0496 0.0292, 0.0475 0.0321, 0.0772 0.0537, 0.1310

Table 3. B3LYP-predicted relative energies [kJ mol 1] for the [C6X6]+

cation radicals. partially fluorinated benzenes. The impurities, mostly
Cation radical Quinoid Bis-allyl D6h symmetry
C6HF5, were as high as 2 mol %. If a large excess of C6F6
structure structure point was used relative to the oxidant, the resulting product would
ACHTUNGRE[C6F6]+ 0 0.4 12[a] contain [C6HF5]+ as well as [C6F6]+, because hydrogen-con-
ACHTUNGRE[C6Cl6]+ 0 0.3 6.7[a] taining fluorobenzenes have lower IPs than C6F6. This result
ACHTUNGRE[C6Br6]+ 0 0.3 4.2[a] could only be avoided by using C6F6 with a purity of 99.9 %
ACHTUNGRE[C6I6]+ 0 or above, and the molar excess used in oxidation reactions
[a] Jahn–Teller stabilization energy at the intrinsic linearly-interpolated should be as low as practically possible (preferably less than
coordinates. a two-fold excess of C6F6).

ACHTUNGRE[C6HF5]+: When one of the six F atoms in C6F6 was replaced

noid [C6F6] cation in [C6F6] ACHTUNGRE[Sb2F11] was the complete op-
+ +
by a H atom, calculations predicted that the separation of
posite, although the differences were only about 10 pm in- the quinoid and bis-allyl isomer energies increased to about
stead of 50 pm. A more-detailed analysis of the cationic···a- 34 kJ mol 1,[20] with the bis-allyl structure becoming the
nionic interactions is given in the Supporting Information. ground state. The compound [C6HF5]+ACHTUNGRE[AsF6] prepared
One experimental problem that should be mentioned herein was a yellow crystalline solid; its EPR spectrum had
before discussing the other benzene cation radicals is that the expected hyperfine structure and resembled the spec-
commercially available C6F6 contained various amounts of trum reported more than 40 years ago.[22] In crystals of this

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 K. Seppelt et al.

Table 4. X-ray and B3LYP-predicted average C C bond lengths for sets of real or idealized symmetry-related compound, there were two
bonds in neutral C6X6 and [C6X6]+ cation radicals [pm].[a] unique [C6F5H]+ cations and
X Neutral C6X6, ACHTUNGRE[C6X6]+ quinoid ACHTUNGRE[C6X6]+ bis-allyl-like ACHTUNGRE[C6X6]+ D6h two unique AsF6 anions in the
D6h geometry geometry geometry geometry asymmetric unit, and the struc-
X-ray DFT X-ray DFT X-ray DFT X-ray DFT
tures of the two cation radicals
F 137.8(2) 138.9 136.8(4)  2, 137.0  2, 137.7(4)  4’ 138.8  4,
were very similar: both cations
141.0(3)  4[b,c] 142.7  4 143.4(3)  2[b,c] 144.8  2
Cl 139.5(5)[d] 139.8 138.2  2, 140.2(3)  4, 139.9  4, had the C2v bis-allyl geometry
144.8  4 144.1(5)  2[b] 144.7  2 (Figure 2). As was the case with
Br 140.1(5)[d] 140.0 138.8  2, 140.0  4, the [C6F6]+ ions, the long and
142.8  4 144.3  2 short C C atomic distances
I 139.9(7)[e] 140.8 139.6(5)  6[f] 139.7  6
were clearly statistically differ-
[a] All data are from this work unless otherwise noted (T = 140 8C). For the X-ray structures, the standard ent, even though the standard
error shown is the standard error for an individual C C distance, not the standard deviation of the average.
[b] Reference [26] (T = 140 8C). [c] [Sb2F11] salt. [d] Reference [29] (T = 173 8C). [e] Reference [37] (T =
errors were higher: the differ-
173 8C). [f] [SbF6] salt. ence between the average of
one set of short C C bond
lengths, 136.8(7) pm, and the
Table 5. X-ray and B3LYP-predicted average C C bond lengths for sets of real or idealized symmetry-related
bonds in [C6HnFm]+ cation radicals [pm].[a] average of the long bond
Compound ACHTUNGRE[C6HnFm]+ quinoid ACHTUNGRE[C6HnFm]+ bis-allyl-like ACHTUNGRE[C6HnFm]+ D3h
lengths, 143.7(7) pm, was about
geometry geometry geometry 10 times the standard error for
X-ray DFT X-ray DFT X-ray an individual C C bond length.
ACHTUNGRE[C6HF5]+ACHTUNGRE[AsF6] 137.1(7)  2, 137.9  2, Furthermore, as observed
143.7(7)  2, 144.8  2, above, the DFT-predicted C C
136.8(7)  2 138.9  2 bond lengths closely matched
2,3,5,6-[C6H2F4]+ACHTUNGRE[SbF6] ·0.5 HF 137.2(3)  4, 137.9  4
the X-ray-determined bond
143.9(3)  2[b] 144.9  2
2,4,6-[C6H3F3]+ACHTUNGRE[SbF6] 142.6  2 144.2  2 140.7(2)  6[c] lengths (Table 5).
141.6  2 138.0  2
136.3  2 138.4  2 2,3,5,6-[C6H2F4]+: Tetrafluoro-
3,4,5,6-[C6H2F4]+ 142.0  2
benzene 2,3,5,6-C6H2F4 was oxi-
136.2  2,
142.1  2 dized to produce crystals of
2,4,5,6-[C6H2F4]+ 141.4  2 both 2,3,5,6-[C6H2F4]+-
136.2  2, ACHTUNGRE[SbF6] ·0.25 HF and 2,3,5,6-
143.5  2 [C6H2F4]+ACHTUNGRE[Sb2F11] . The EPR
[a] All data are from this work (T = 140 8C). For the X-ray structures, the standard error shown is the stan- spectrum of the 2,3,5,6-
dard error for an individual C C distance, not the standard deviation of the average. [b] The three correspond- [C6H2F4]+ cation radical was
ing distances for neutral 2,3,5,6-C6H2F4 (T = 140 8C) are 138.2(1), 138.3(1), and 138.3(1) pm. [c] The B3LYP-
predicted difference in energies between the quinoid and bis-allyl (ground state) structures of 2,4,6-[C6H3F3]+
a straightforward quintet (aF =
cation is 1.2 kJ mol 1. 25.6 G) of triplets (aH = 1.0 G).
A single crystal of 2,3,5,6-
[C6H2F4]+ACHTUNGRE[SbF6] gave the more
precise X-ray structure, so only these data will be discussed

Figure 1. The two [C6F6]+ cation radicals in the crystal of
[C6F6]+ [Sb2F11] , ellipsoids set at 50 % probability (see reference [26]).
Left: the quinoid cation. Right: the bis-allylic cation. Only the unique C
C bond lengths [pm] are shown. The average C C distance in neutral
C6F6 is 137.8(2) pm (average of nine values; see the Supporting Informa-
tion).
Figure 2. The [C6HF5]+ ion in [C6HF5]+ [AsF6] ; ellipsoids set at 50 %
probability, except for the H atom, which is shown as a sphere of arbitra-
ry size. The two distances [pm] given for each C C bond refer to the two
crystallographically independent cations in the asymmetric unit. The
numbers in italics are the DFT-predicted C C bond lengths for the gas-
phase cation radical.

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Halogenated Benzene Cation Radicals
herein (although the cations in both structures had very sim-
ilar geometries).
There were four independent 2,3,5,6-[C6H2F4]+ cations,
four [SbF6] anions, and two HF molecules in the asymmet-
ric unit. All of the cations possessed the bis-allyl geometry
(Figure 3), which agreed with the predicted geometry
(Table 5, also see the Supporting Information). The C C
bond lengths in the cations were compared with neutral
2,3,5,6-C6H2F4, which was readily obtained as single crystals
owing to its relatively high melting point. The C C bond
lengths were all statistically the same in the structure of this
neutral tetrafluorobenzene (138.23(9)–138.33(9) pm; see the
Supporting Information, Figure SI-4).
+ crystal. Figure 4 shows the columnar arrangement of alter-
Figure 3. The 2,3,5,6-[C6H2F4] cation radical in
[C6H2F4]+ [SbF6] ·0.25 HF; ellipsoids set at 50 % probability, except for
the H atoms, which are shown as spheres of arbitrary size. The first four
numbers are the C C bond lengths [pm] for the four crystallographically
independent cations in the lattice. Only the unique C C bond lengths are
shown. The first number in italics is the DFT-predicted C C distance for
the gas-phase cation radical; the second number in italics is the DFT-pre-
dicted C C distance for the neutral precursor 2,3,5,6-C6H2F4 (also see the
Supporting Information).
2,4,6-[C6H3F3]+: Owing to the D3h symmetry of the parent
benzene, 2,4,6-C6H3F3, the corresponding cation should ex-
hibit a Jahn–Teller distortion. Again, the two possible iso-
mers, quinoid and bis-allyl, should be very close in energy,
with the quinoid form possibly being the minimum
(Table 3). Oxidation of 2,4,6-C6H3F3 with [O2]+ACHTUNGRE[Sb2F11] and
[O2]+ACHTUNGRE[AsF6] in liquid HF produced 2,4,6-[C6H3F3]+SbF6
and 2,4,6-[C6H3F3]+ACHTUNGRE[AsF6] , respectively, as ruby-red,
needle-shaped crystals in almost quantitative yield. Interest-
ingly, the use of [O2]+ACHTUNGRE[Sb2F11] as the oxidant yielded the
[SbF6] salt, even in the presence of a large excess of SbF5.
Both salts resulted in very precise crystal-structure deter-
minations. The crystals were isomorphous, and the space
group R3̄c resulted in the cations and anions being in special
positions. This structure required rigorous D3d symmetry for
the anions and, more importantly, rigorous D3h symmetry
for the 2,4,6-[C6H3F3]+ cation radical. Although distorted
cations that were three-fold disordered could not be exclud-
ed, the small and relatively symmetric thermal displacement
parameters (at 140 8C) did not give any indication of disor-
der. We believe that the lack of an observable Jahn–Teller
distortion in the cation, despite the prediction that the
cation should be distorted, could be explained by the unusu-
Chem. Eur. J. 2012, 00, 0 – 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 4. Left: The formula unit in the structure of 2,4,6-
[C6H3F3]+ [SbF6] ; ellipsoids set at 50 % probability, except for the H
atoms, which are shown as spheres of arbitrary size. The rigorously
planar cation is in the plane of the page and the SbF6 anion is below the
plane of the page. Only the unique C C, C H, and C F distances are
shown. The corresponding distances in the structure of 2,4,6-[C6H3F3]+-
ACHTUNGRE[AsF6] are 140.5(2), 84(4), and 131.3(3) pm, respectively. Right: The cat-
ionbanion packing along the threefold crystallographic axis in 2,4,6-
[C6H3F3]+ACHTUNGRE[SbF6] . All of the C1···F2 distances shown are 292.7(1) pm. Se-
lected interatomic distance [pm] and angles [8]:Sb–F 187.90(8);
F2···C1···F2’ 173.88(8), F-Sb-F 90.41(4), 89.59(4), and 180.00(4).
ally symmetric and efficient cation···anion packing in the
nating cations and anions along the hexagonal axis of the
rhombohedral crystal. There were relatively short contacts
(292.7(1) pm) between the three benzene C(F) atoms and
the anion F atoms; this was a sensible result because the
C(F) atoms were expected to carry most of the positive
charge of the cation. The substantial charge-neutralization
and concomitant large lattice energy caused by the efficient
ion packing sterically enforced the three-fold symmetry on
the 2,4,6-[C6H3F3]+ ion, despite the electronically-preferred
distorted geometry. This result also explains why only the
SbF6 compound could be isolated: the low solubility of
2,4,6-[C6H3F3]+ACHTUNGRE[SbF6] drove the equilibrium [Sb2F11] Q
[SbF6] +SbF5 to the right, even when the oxidation with
[O2]+ACHTUNGRE[Sb2F11] was carried out with a large excess of SbF5.
We were not able to isolate a salt of the 2,4,6-[C6H3F3]+
cation with a lower-symmetric anion, either by starting with
an alternative oxidant or through an anion-exchange reac-
tion following the oxidation.
Our current interpretation of the structure of this com-
pound is that the electrostatic interaction provides enough
energy to hold the cation in the observed symmetric geome-
try. Our calculations predicted that the energy needed to
overcome the Jahn–Teller distortion was only about
12 kJ mol 1.
ACHTUNGRE[C6Cl6]+ and [C6Br6]+: As expected, C6Cl6 and C6Br6 were
easier to oxidize than the fluorinated benzenes (IP: 9.13(3)
and 8.80 eV, respectively; see the Supporting Information,
Table SI-1). Neat SbF5 alone could also act as the oxidant
for these hexahalobenzenes. Recrystallization from SO2FCl
afforded crystals of [C6Cl6]+ACHTUNGRE[Sb2F11] and [C6Br6]+ACHTUNGRE[Sb2F11] .
The crystal structure of [C6Cl6]+ACHTUNGRE[Sb2F11] was precise enough
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 K. Seppelt et al.

to draw definite conclusions about the geometry of the Hypothetically, if the [C6Cl6]+ cation radical had the quinoid
[C6Cl6]+ cation radical. However, the crystallographic char- geometry, we would expect the C2 atoms to have closer
acteristics of [C6Br6]+ACHTUNGRE[Sb2F11] were poor. The [C6Br6]+ and/or a greater number of contacts with the F atoms of the
cation seemed to have a quinoid structure, as predicted by anions relative to the C1 and C3 atoms.
computation, but better structural data are needed.
However, the [C6Cl6]+ cation had a bis-allyl geometry CHTUNGRE[A C6I6]+: C6I6 was the benzene with the lowest ionization po-
(Figure 5), with two long C C bonds (144.5(5) and tential studied herein (IP = 7.9 eV; see the Supporting Infor-
mation, Table SI-1). Several attempts to oxidize C6I6 have
been reported, and black products were always observed in
H2O2/CF3SO3H solutions. These products have been de-
scribed as [C6I6]2+ salts.[31, 32] The crystal structure of a com-
pound with the formula [C6I62+]ACHTUNGRE[(CF3SO3 )2] was described
in a PhD dissertation,[33] but, to the best of our knowledge,
such a structure has not been published elsewhere. Herein,
we oxidized C6I6 by using SbF5 or AsF5 in HF, which indeed
resulted in such black precipitates. However, single crystals
were obtained with the compositions [C6I6]+ACHTUNGRE[SbF6] and
[C6I6]+ACHTUNGRE[AsF6] .[34] These two salts were isomorphous.
The [C6I6]+ cation radicals in both structures had undis-
torted hexagonal geometries (Figure 6). Because the packing
arrangements of the ions were quite irregular (unlike the sit-
uation in the 2,4,6-[C6H3F3]+ salts), the symmetric geome-
tries observed for the [C6I6]+ cation radicals in [C6I6]+
[SbF6] and [C6I6]+ [AsF6] were quite clearly not a result of
differential cation···anion interactions. In fact, a symmetric
geometry was predicted by our calculations. The HOMO of
C6I6 was a non-bonding A1g iodine-centered orbital that was
Figure 5. The structure of [C6Cl6]+ [Sb2F11] , which shows two symmetry- represented by a combination of the six iodine p-orbitals
related anions and one cation radical; ellipsoids set at 50 % probability.
Selected interatomic distances [pm]: C1–C2 139.9(3), C1–C1A 144.5(5),
lying in the molecular plane in an antibonding manner.
C2–C3 140.5(3), C3–C3A 144.1(5), C1···F4 317.3(3), C1···F5B 300.4(3), Therefore, one-electron oxidation of C6I6 removed an elec-
C2···F5B 312.5(3), C3···F3 326.6(3), C3···F2B 319.1(3). tron largely from the I atoms, not from the C atoms (i.e.,
not from a degenerate C C p orbital), and should not result
144.1(5) pm) and four shorter C C bonds (in the range in a Jahn–Teller distortion of the molecule (unlike the other
139.9(3)–140.5(3) pm). The three unique C C distances in halogens, the ionization potential of an I atom, 10.45 eV, is
neutral C6Cl6 were statistically the same and ranged from lower, not higher, than that of a C atom, 11.26 eV). Further-
138.6(5)–140.0(5) pm at 173 8C[29] and from 139.1(3)– more, oxidation of the [C6I6]+ cation radical should result in
[30]
139.5(3) pm at 24(1) 8C. Although this result contradicted a [C6I6]2+ dication that also has a hexagonal geometry. It has
the theoretical prediction that the ground state of the been suggested that removal of the two A1g electrons from
[C6Cl6]+ cation should adopt the quinoid geometry, the cal- C6I6 would result in a s-aromatic ring-current in the [C6I6]2+
culated difference in energy was only 0.24 kJ mol 1 between dication,[31, 32, 35, 36] in contrast to the situation for [C6Cl6]2+.[37]
the quinoid ground state and
the bis-allyl transition state.
There were two C···F(Sb) inter-
actions for the C1 atom and
two for the C3 atom, which
ranged from 300.4(3) to
326.6(3) pm, but only one
C2···F(Sb) interaction
(312.5(3) pm), as expected for
a bis-allyl structure. In fact, it
can be argued that the C2···F5B
contact was really a conse-
quence of the proximity of the
F5B atom to the C1 atom
Figure 6. Left: The [C6I6]+ cation radical in [C6I6]+ [AsF6] and [C6I6]+ [SbF6] , which are isostructural; ellip-
(C1···F5b = 300.4(3) pm), which soids set at 50 % probability. The top number refers to the [AsF6] salt and the bottom number to the [SbF6]
required that the F5B atom salt. Only the unique C C distances [pm] are shown. Right: The crystal structure of [C6I6]+ [HACHTUNGRE(SO3CF3)2] .
must be close to the C2 atom. The anion has a short O(H)···O distance of 243.9 pm.

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Halogenated Benzene Cation Radicals
FULL PAPER
The average intramolecular I···I distance for the [C6I6]+ zenes occasionally resulted in the formation of salts of the
cation radical (347.8 pm) was only marginally shorter than perhalogenated benzenium cations [C6Cl7]+, [C6Cl5F2]+, and
the corresponding average distance in neutral C6I6 [C6Br5F2]+. These compounds will be reported in a future
[37]
(351.3 pm). This was a sensible result, because the as- report.
sumed half-bond between the I atoms in [C6I6]+, spread as
over six intramolecular I···I interactions, would not be ex- Computational results: Perhalogenated benzenes: Our DFT-
pected to result in a significant amount of shortening. Fur- predicted and X-ray structural parameters for the neutral
thermore, the shortening was not due to differences in the benzenes C6X6 (D6h symmetry; X = F, Cl, Br, I) and the
displacements of the I atoms from the C6 planes of C6I6 and cation radicals [C6X6]+ are listed in Table 4. At the level of
+
[C6I6] : in both cases, the mean displacement was only about theory used in this work, the C X bond lengths increased
4 pm. from 1.331  in C6F6 to 2.123  in C6I6, as did the intramo-
We believed that the compound previously reported to be lecular X···X distance, from 2.270  to 3.531 . Interesting-
[C6I6]2+ACHTUNGRE[(CF3SO3 )2] was probably [C6I6]+[HACHTUNGRE(CF3SO3)2] . ly, the aromatic-ring C C bond lengths also increased as the
Dissolution of [C6I6]+ACHTUNGRE[AsF6] in CF3SO3H resulted in the size of the halogen atoms increased, from 1.389  in C6F6 to
formation of small amounts of crystalline [C6I6+][H- 1.408  in C6I6. The two-fold degenerate HOMO in C6F6
ACHTUNGRE(CF3SO3)2] , which we analyzed by X-ray crystallography. was a pair of C C p orbitals, labeled as B (a bis-allyl-like or-
Our compound and the compound previously reported as bital) and Q (a quinoid-like orbital) in Figure 7. The bis-
[C6I6]2+ACHTUNGRE[(SO3CF3 )2][33] were
crystallographically identical in
all respects. As in the structures
of [C6I6]+ACHTUNGRE[SbF6] and [C6I6]+-
ACHTUNGRE[AsF6] , the monovalent cation
radical [C6I6]+ in [C6I6+][H-
ACHTUNGRE(CF3SO3)2] had a symmetric
hexagonal geometry. The over-
looked hydrogen atom in the
previously reported crystal
structure was not only detected
in this work by a difference
Fourier analysis, its presence
was also obvious because of the
short O···O distance (243.9 pm),
which is the hallmark of
a strong O H···O hydrogen
bond.[38] Furthermore the two
S O bonds that participated in Figure 7. The HOMO energies for C6X6 (X = F, Cl, Br, and I) are shown in a partial MO diagram. B = bis-allyl
the hydrogen bond were elon- orbital; Q = quinoid orbital; XX3* = totally symmetric antibonding in-plane halogen-atom p-orbital with three
gated by 5–8 pm relative to the nodal planes. Orbital plots for C6F6 are shown as an example (B3LYP/tzvpp).
other S O bonds.
The absence of an observable
EPR spectrum was previously cited as evidence for the exis- allyl orbital had a perpendicular nodal plane that bisected
tence of the diamagnetic [C6I6]2+ dication.[33] However, in opposite C C bonds, whilst the quinoid orbital had a perpen-
our hands, all of the C6I6+ salts exhibited very broad EPR dicular nodal plane that included two para-C atoms. The
signals at 196 8C. Taken together, our crystallographic and third C C p orbital was HOMO-1. Below the energy of
spectroscopic results led us to conclude that the [C6I6]2+ di- HOMO-1 in C6F6 were six orbitals that were composed of
cation remains an unknown species. Nevertheless, if it is linear combinations of in-plane X-atom p orbitals (X = F).
ever isolated, it will probably be found to have a symmetric One of these six orbitals (XX3*, Figure 7) was important be-
hexagonal geometry like C6I6 and [C6I6]+, as predicted by cause its energy was especially sensitive to the nature of the
calculations. halogen atom. The XX3* energy was 0.175 below the B/Q
energy for C6F6, but this difference decreased to 0.039 for
Halogenated benzenium ion salts: Salts of benzenium cat- C6Cl6 and to 0.003 for C6Br6. For C6I6, XX3* was the
ions are intermediates in electrophilic aromatic substitution HOMO and the degenerate B/Q orbital was HOMO-1.
reactions and therefore have been studied extensively. In The molecular orbital diagrams indicated that Jahn–
many cases, they can be isolated, particularly if electron-do- Teller-distorted geometries should be found for [C6X6]+ with
nating substituents are present.[39] The parent cation [C6H7]+ X = F, Cl, and Br but not for X = I. Two distorted cations,
was recently isolated by using a weakly-coordinating carbor- a compressed one with the quinoid orbital as a singly occu-
ane anion.[39] Our oxidation reactions of halogenated ben- pied orbital and an elongated one with the bis-allyl orbital

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 K. Seppelt et al.

as a singly occupied orbital, were found for [C6X6]+, with

X = F, Cl, and Br. The compressed (quinoid) cation geome-
tries were classified as minima, with the elongated (bis-allyl)
geometries as transition states. The [C6I6]+ cation retained
the D6h symmetry of neutral C6I6. The behavior of the orbi-
tals was as expected from the molecular orbital diagram of
the neutral molecule. The difference between the quinoid
and bis-allylic orbitals was about 0.13–0.18 for the cations
(X = F, Cl, Br), and the XX3* orbitals became closer in
energy to the quinoid and bis-allylic orbitals. Significantly,
the barrier between the distorted ground-state geometries
and the hexagonal geometry decreased in the order
[C6F6]+ > [C6Cl6]+ > [C6Br6]+.
Linearly interpolated intrinsic coordinates (LIICs) for the
Figure 8. The quinoid- and bis-allyl-distorted cation-radical structures are
cation radicals [C6F6]+, [C6Cl6]+, and [C6Br6]+ were generat- connected by two paths. The path through the D6h symmetry point can
ed to calculate the Jahn–Teller stabilization energy, eJT, as be described by calculating the LIICs; the other path, which leads from
the difference EACHTUNGRE(D6h) EACHTUNGRE(D2h), where EACHTUNGRE(D2h) was the energy the bis-allyl cation as a transition state to the minimum-energy quinoid
of the bis-allyl cation radical. For C6F6+ this difference was cation, can be calculated by using IRCs. The combined paths can be used
to construct a potential energy surface for the system, which has the ap-
about 12 kJ mol 1, which decreased to 6.7 kJ mol 1 for
pearance of a “Mexican hat” (see reference [26]).
[C6Cl6]+ and to 5.4 kJ mol 1 for [C6Br6]+. The bis-allyl and
quinoid structures were nearly isoenergetic. In [C6F6]+, their
energy difference was only 0.4 kJ mol 1, and the difference because the maximum difference in the C C bond lengths
was even smaller for [C6Cl6]+ and [C6Br6]+ (Table 3). These was smaller than 1 pm. Inspection of the molecular orbital
values were certainly within the uncertainty of the computa- diagrams for these molecules showed that the bis-allyl and
tional methods used, but the calculated trend was independ- quinoid p orbitals were no longer degenerate. In C6HF5 and
ent of the basis set and the method used. A calculation 2,3,5,6-C6H2F4, the quinoid orbital was the HOMO, and so
using intrinsic reaction coordinates (IRCs) offered a possible removing an electron would lead to a bis-allyl-distorted
reaction path from the bis-allylic cation to the quinoid cation radical. In 2,4,5,6-C6H2F4 and 3,4,5,6-C6H2F4, the bis-
cation. In both paths, the LIICs and the IRCs connected the allyl orbital was the HOMO and a quinoid-distorted cation
two distorted structures. These are the two typical paths for radical would be expected (Figure 9).
the interconversion of geometries in such systems,[19] and
they can be combined to calculate a potential energy surface
(Figure 8).
The Jahn–Teller distortions in the [C6X6]+ cation radicals
were quantified geometrically by comparing the difference
between the elongated and compressed C C bond lengths;
we found that this difference was predicted to decrease
from 6.0 pm for both types of [C6F6]+ cations to 4.8 and
4.6 pm for the bis-allyl and quinoid [C6Cl6]+ cations, respec-
tively, to 4.3 and 4.0 pm for the bis-allyl and quinoid
[C6Br6]+ cations, respectively. Experimentally, the observed
differences were 6.0(5) and 5.4(4) pm for the bis-allyl
[C6F6]+ cation in [C6F6]+ACHTUNGRE[Sb2F11] and 4.6(6) and 3.6(6) pm
for the bis-allyl [C6Cl6]+ cation in [C6Cl6]+ACHTUNGRE[Sb2F11] .
The average Mulliken charge on the F atoms in [C6F6]+
was predicted to be slightly negative ( 0.1 e). In contrast, it
was slightly positive (+0.1 e) on the Cl and Br atoms in
Figure 9. A partial molecular orbital diagram for fluorinated benzenes
[C6Cl6]+ and [C6Br6]+ and +0.25 e on the I atoms in [C6I6]+. showing the high-energy occupied orbitals, including the bis-allyl (B) and
Both the Mulliken charge and the occupancy of the orbitals quionid (Q) p orbitals. Orbital plots for C6F6 are shown as an example
indicated a significant positive charge on the I atoms in the (B3LYP/tzvpp).
cation radical.

Partially fluorinated benzene derivatives: The molecular
symmetry of the partially-fluorinated neutral molecules
C6HF5, 2,3,5,6-C6H2F4, and 2,4,5,6-C6H2F4 was D2h, and for
3,4,5,6-C6H2F4 it was C2v. Nevertheless, the hexagonal C C
framework in all four molecules had effective D6h symmetry
The explanation of these differences is as follows: In C6F6,
the bis-allyl and quinoid p orbitals contained an antibonding
contribution from the in-plane F atom p-orbitals, thus rais-
ing their energy. For the bis-allyl p orbital, two large and
four small out-of-plane F atom p-orbital contributions were

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Halogenated Benzene Cation Radicals
present, whilst for the quinoid p orbital, four large out-of-
plane contributions were present. In C6HF5 and 2,3,5,6-
C6H2F4, one and two of the large out-of-plane contributions
in C6F6 were missing due to the presence of the H atoms, re-
spectively. This result lowered the energy of the bis-allyl or-
bital, thereby making the quinoid orbital the HOMO. In
3,4,5,6-C6H2F4 and 2,4,5,6-C6H2F4, both orbitals were stabi-
lized as follows: for the bis-allylic orbital, two small anti-
bonding F atom p-orbital contributions were missing, and
for the quinoid orbital two large antibonding F atom p-orbi-
tal contributions were missing. Thus, the quinoid p orbital
was stabilized to a greater extent, and the bis-allyl orbital
became the HOMO.
After removing an electron from the neutral molecules,
structural optimizations were performed, starting with the
same symmetry. In each case, a distorted cation was found.
As expected, [C6HF5]+ and 2,3,5,6-[C6H2F4]+ had bis-allyl
geometries and 2,4,5,6-[C6H2F4]+ and 3,4,5,6-[C6H2F4]+ had
quinoid geometries. The difference for the bis-allylic and
quinoid orbitals increased from the neutral compounds
(average: 0.016) to the cation radicals (average: 0.197), but
the order was the same. These results were in full agreement
with previous calculations reported for such systems.[20] Fol-
lowing ionization, the molecules were predicted to exhibit
distorted bis-allyl geometries, with maximum differences in
C C distance of 6.4–7.3 pm. The differences in experimental
C C bond lengths for the [C6HF5]+ and 2,3,5,6-[C6H2F4]+
cations agreed with the calculated values to within ( 2) and
( 1) pm, respectively (these two cation radicals did have
bis-allyl geometries in the solid state).
Finally, all of our attempts to find other relatively stable
distorted geometries for the cation radicals were unsuccess-
ful, including LIICs between other assumed geometries and
for geometries distorted along symmetry-reducing coordi-
nates.
Experimental Section
Caution: Handling anhydrous HF, dioxygenyl salts, SbF5, and AsF5 re-
quires eye and skin protection.
Reagents and solvents: The following reagents were purchased from the
indicated vendor: C6HF5, 2,4,6-C6H3F3 and 2,3,5,6-C6H2F4 (ABCR
GmbH), C6Cl6 and C6Br6 (Sigma–Aldrich Chemie GmbH), elemental As
(ABCR GmbH), SO2Cl2 (Merck Schuchardt), SbF5 (Fluorochem Ltd.),
NH4F (E. Merck), KI (Acros Organics), HIO4 (H5IO6 ; E. Merck),
CF3COOH (Merck Schuchardt), CF3SO3H (Merck Schuchardt; distilled
from P2O5 (Sigma Aldrich GmbH)). The five benzenes were checked for
purity by NMR spectroscopy and were redistilled or resublimed as neces-
sary. C6I6 was prepared by treating benzene with periodic acid in the
presence of potassium iodide.[40] Arsenic pentafluoride was prepared by
passing F2 gas over elemental arsenic.[41] [O2]+ [AsF6] and [O2]+ [Sb2F11]
were prepared from O2, F2, and either AsF5 or SbF5 by irradiation with
UV light.[42] Solvent SO2ClF was prepared by treating a mixture of
SO2Cl2 and NH4F with CF3COOH.[43] Perfluorohexane (ABCR GmbH)
was dried and purified by treatment with KF followed by
[XeF]+ [Sb2F11] . Anhydrous HF was vacuum-distilled into a stainless
steel cylinder containing BiF5 to remove any residual H2O. SbF5 was
vacuum-distilled twice by using a glass vacuum line with a 30 8C trap.
The resulting liquid was clear, colorless, and highly viscous.
Chem. Eur. J. 2012, 00, 0 – 0  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
[C6F6]+ [Os2F11] and [C6F6]+ [Sb2F11] were prepared according to litera-
ture procedures.[26]
Physical methods: X-band EPR spectra were recorded on a Bruker ER
200 D-SRC spectrometer equipped with an ER 4111 variable-tempera-
ture unit that allowed for low-temperature measurements. Except for the
[C6I6]+ salts, all samples were freshly prepared in either SO2 or SO2ClF
(Table 1) and sealed in 4 mm O.D. PFA tubes. Samples of [C6I6]+ [AsF6]
and [C6I6]+ [SbF6] were weighed into PFA tubes, then anhydrous
CF3SO3H was added, and the tubes were sealed under an Ar atmosphere
(PFA = poly(perfluorether-tetrafluorethylene)). Single crystals suitable
for X-ray diffraction were mounted on a Bruker Smart 2000 diffractome-
ter (MoKa radiation) under oxygen- and moisture-free conditions at tem-
peratures below 100 8C by using a special device of local design. All
data collections were performed at 140 8C. After semiempirical absorp-
tion corrections, the structures were solved and refined by using the pro-
gram SHELXL.[44] Non-hydrogen atoms were refined anisotropically; H
atoms were refined isotropically. Relevant data collection and refinement
parameters are listed in Table 2.
Synthesis of new compounds: General procedures: Moisture-sensitive
nonvolatile materials were handled in a glovebox in an inert atmosphere
of less than 0.1 ppm H2O and O2. Volatile materials were handled in
glass or stainless steel vacuum lines as appropriate. The oxidation reac-
tions were generally carried out in 8 mm PFA tubes that were connected
to a vacuum line. Weighed portions of the nonvolatile oxidants were
transferred into the tube in the glovebox, after which the solvent and the
benzene reagent were added by using the vacuum line. The oxidation re-
actions frequently occurred rapidly even at low temperatures, and were
signaled by the formation of an intense color. The cation-radical-salt
products often decomposed at 25 8C, with the concomitant loss of color.
ACHTUNGRE[C6HF5]+ [AsF6] : A sample of C6HF5 (600 mg, 3.57 mmol) was cooled to
48 8C, the melting point of this compound. Small portions of [O2]+-
ACHTUNGRE[AsF6] (total 100 mg, 0.453 mmol) were added under an Ar atmosphere;
the mixture was shaken carefully after each portion (about 5 mg) was
added. The resulting green suspension was warmed to 35 8C and all of
the volatile compounds were removed under vacuum. A yellow powder
was obtained in 70 mg (43 % based on [O2]+ACHTUNGRE[AsF6] ). The dry product
decomposed within minutes at 25 8C. Recrystallization from anhydrous
HF (4 mL) at 78 8C afforded large yellow needles after 24 h.
2,3,5,6-[C6H2F4]+ ACHTUNGRE[SbF6] : A mixture of anhydrous C6F14 (4 mL) and
2,3,5,6-C6H2F4 (60 mg, 0.4 mmol) was cooled to 78 8C and small por-
tions of [O2]+ACHTUNGRE[Sb2F12] (total 200 mg, 0.413 mmol) were added under an
Ar atmosphere; the mixture was shaken carefully after each portion
(about 5 mg) was added. The resulting yellow–green suspension was
warmed to 45 8C and all of the volatile compounds were removed
under vacuum. The product, as a yellow powder, decomposed immediate-
ly at 25 8C and was recrystallized from a green solution in anhydrous HF
(2 mL) as green crystals after 1 week at 78 8C.
2,4,6-[C6H3F3]+ ACHTUNGRE[AsF6] : [O2]+ACHTUNGRE[AsF6] (100 mg, 0.453 mmol) and AsF5
(about 2 mL, 4.3 g, 25 mmol) were mixed in a PFA tube. The volatile
compound 2,4,6-C6H3F3 (54 mg, 0.41 mmol) was added to this mixture at
196 8C. Warming the mixture to 25 8C afforded a clear, wine-red solu-
tion (note that the compound did not decompose rapidly at 25 8C).
Slowly cooling this solution to 78 8C yielded red–brown crystals. Anhy-
drous HF and SO2ClF were also used as solvents with similar results.
2,4,6-[C6H3F3]+ ACHTUNGRE[SbF6] : [O2]+ACHTUNGRE[Sb2F11] (100 mg, 0.206 mmol) was dis-
solved in anhydrous HF (2 mL) at 25 8C in a PFA tube. The mixture was
cooled to 196 8C and 2,4,6-C6H3F3 (26 mg, 0.20 mmol) was added by
vacuum transfer. The mixture was slowly warmed to 25 8C, and produced
the same wine-red solution as described above. Slow cooling to 78 8C
yielded dark-brown needle-shaped crystals.
ACHTUNGRE[C6Cl6]+ ACHTUNGRE[Sb2F11] : C6Cl6 (50 mg, 0.18 mmol) was dissolved in SbF5
(100 mg, 0.461 mmol) at 25 8C in a PFA tube, thereby forming a dark-
blue solution after 15–30 min. The solution was frozen at 196 8C and an-
hydrous HF (2 mL) was added by vacuum transfer. The mixture was
slowly warmed to 0 8C, and afforded a clear, dark-blue solution. Slow
cooling of this solution to 78 8C resulted in the formation of dark-blue
crystals.
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ACHTUNGRE[C6Br6]+ ACHTUNGRE[Sb2F11] : C6Br6 (50 mg, 0.091 mmol) was dissolved in SbF5
(100 mg, 0.461 mmol) at 25 8C in a PFA tube, thereby forming a dark-
green solution after 2–5 min. The solution was frozen at 196 8C and
SO2ClF (2 mL) was added by vacuum transfer. The mixture was slowly
warmed to 0 8C and afforded a clear, dark-green solution. Slow cooling
of this solution to 78 8C resulted in the formation of black crystals. a =
802.9(5), b = 855.3(5), c = 874.0(5) pm; a = 63.12(1), b = 76.13(1), g =
63.088; V = 476.9(5)  106 pm3 ; Z = 1; disordered [Sb2F11] anion; R1 =
0.10; wR2 = 0.3202.
ACHTUNGRE[C6I6]+ ACHTUNGRE[SbF6] : SbF5 (0.42 g, 1.94 mmol), C6I6 (0.5 g, 0.60 mmol), and an-
hydrous HF (2.0 mL) were mixed in a PFA tube at 25 8C until a deep-
blue precipitate had formed. All volatile compounds were removed
under vacuum to afford a deep-blue powder in quantitative yield. A por-
tion (20 mg) of the powder was dissolved in anhydrous CF3SO3H (2 mL)
and heated to 200 8C for 5 min. Slow cooling of the hot solution to 25 8C
resulted in the formation of deep-blue needle-shaped crystals. The com-
pound was stable at 25 8C under an inert atmosphere, but it decomposed
within 10 min when exposed to air.
ACHTUNGRE[C6I6]+ ACHTUNGRE[AsF6] : AsF5 (4.00 g, 23.5 mmol), C6I6 (1.00 g, 1.20 mmol), and
anhydrous HF (1.3 mL) were mixed in a PFA tube at 78 8C until
a deep-blue precipitate had formed. All volatile compounds were re-
moved under vacuum to afford a deep-blue powder in quantitative yield.
A portion (20 mg) of the powder was dissolved in anhydrous CF3SO3H
(2 mL) and heated to 200 8C for 5 min. Slow cooling of the hot solution
to 25 8C resulted in the formation of deep-blue needle-shaped crystals.
The compound was stable at 25 8C in an inert atmosphere, but it decom-
posed within 10 min when exposed to air.
ACHTUNGRE[C6I6]+ ACHTUNGRE[CF3SO3] : When [C6I6]+ACHTUNGRE[AsF6] (120 mg) was heated to 145 8C
under high vacuum (in an attempt to sublime the salt intact), the sample
started to slowly decompose into orange C6I6, purple I2, and other un-
identified products without any indication of the sublimation of [C6I6]+-
ACHTUNGRE[AsF6] . The apparatus was cooled to 25 8C after approximately half of
the sample had been converted into C6I6. To recover the remaining unde-
composed sample of [C6I6]+ACHTUNGRE[AsF6] , a small amount of anhydrous
CF3SO3H was added under an Ar atmosphere. After 2 days at 25 8C,
deep-blue crystals of [C6I6]+ACHTUNGRE[CF3SO3] had crystallized out of this solu-
tion.
Quantum-chemical calculations: Halogenated benzenes C6X6 (X = F, Cl,
Br, I) and partially-fluorinated benzenes C6HF5 and 2,3,5,6-, 2,4,5,6-, and
3,4,5,6-C6H4F2 as well as their corresponding single-positively charged
cation radicals were investigated by quantum-chemical calculations by
using the B3LYP DFT-functional[45] and the TZVPP basis set.[46] For I
atoms, the Def2-ECP28 pseudo-potential[47] was applied. Test calculations
for C6F6 and [C6F6]+ with different basis sets and different functionals re-
sulted in similar relative energies, as did the B3LYP/TZVPP and
CCSD(T) levels of theory.[26] The structures of the neutral molecules and
the cation radicals were optimized. The two energetically similar isomers
with the same symmetry were calculated by starting with models that had
4 C C bond lengths longer than 2 C C bond lengths and vice versa. Fre-
quency calculations were performed to determine whether the optimized
structures were a true minimum or a transition state. The program pack-
ages used were GAUSSIAN 03[48] and TURBOMOLE5v10.[49]
One reviewer brought to our attention a distantly related Jahn–Teller
isomer problem: the [CuACHTUNGRE(NO2)6]4 anion has been found to exist both as
an elongated and a compressed octahedron, depending on the type of
cation. Furthermore there even exists a regular octahedral anion that is
generated by a dynamic Jahn–Teller effect.[50, 51]
CCDC-703472 ([C6F6]+ [Os2F11] ), CCDC-703473 ([C6F6]+ [Sb2F11] ),
CCDC-703623 ([C6F6]), CCDC-844888 ([C6HF5]+ [AsF6] ), CCDC-844885
([C6H2F4]+ [SbF6] ·0.5 HF), CCDC-844884 ([C6H2F4]), CCDC-844886
([C6H3F3]+ [AsF6] ), CCDC-844887 ([C6H3F3]+ [SbF6] ), CCDC-844883
([C6Cl6]+ [Sb2F11] ), CCDC-844882 ([C6Br6]+ [Sb2F11] ), CCDC-844889
([C6I6]+ [AsF6] ), CCDC-844890 ([C6I6]+ [SbF6] ), and CCDC-844891
([C6I6]+ [HS2O6C2F6] ) contain the supplementary, crystallographic data
for this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
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K. Seppelt et al.
Acknowledgements
This work was made possible by the Deutsche Forschungsgemeinschaft
(Graduiertenkolleg “Fluorine as a Key Element”), the Fonds der Chemi-
schen Industrie, and a DFG grant (to M.K.). Research internship stu-
dents C. Noufele and K. Schulz performed preliminary calculations.
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Received: September 21, 2011
Revised: January 18, 2012
Published online: && &&, 0000
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 K. Seppelt et al.

Jahn–Teller distortion The new radicals: The [C6I6]+ radical

cation is, in contrast to all other
M. J. Molski, D. Mollenhauer, S. Gohr, [C6X6]+ radical cations presented
B. Paulus, M. A. Khanfar, H. Shorafa, herein, not Jahn–Teller distorted.
S. H. Strauss, K. Seppelt* . . . &&&&—&&&&
Halogenated Benzene Cation Radicals

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