Angewandte
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Carbocations
Crystal Structure Determination of the Pentagonal-Pyramidal
Hexamethylbenzene Dication C6(CH3)62+
Moritz Malischewski* and K. Seppelt
Dedicated to Professor Karl Otto Christe on the occasion of his 80th anniversary
Abstract: In contrast to the well-known 2-norbornyl cation, the
structure of which was a matter of long debate until its
pentacoordinated nature was recently proven by an X-ray
structure, the pentagonal-pyramidal dication of hexamethyl-
benzene has received considerably less attention. This species
was first prepared by Hogeveen in 1973 at low temperatures in
magic acid (HSO3F/SbF5), for which he proposed a non-
classical structure (containing a hexacoordinated carbon)
based on NMR spectroscopy and reactivity studies, but no X-
ray crystal structure has been reported. C6(CH3)62+ can be
obtained through the dissolution of hexamethyl Dewar ben-
zene epoxide in HSO3F/SbF5 and crystallized as the SbF6 salt
upon addition of excess anhydrous hydrogen fluoride. The
crystal structure of C6(CH3)62+ (SbF6 )2·HSO3F confirms the
pentagonal pyramidal structure of the dication. The apical
carbon is bound to one methyl group (distance 1.479(3) ) and
to the five basal carbon atoms (distances 1.694(2)–1.715(3) ).
The tetravalency of carbon and the hexagonal-planar ring
structure of benzene are fundamental axioms of organic
chemistry, and were developed 150 years ago by Kekul.[1, 2]
Chemists have long been fascinated by finding exceptions
from these rules. Starting in the 1960s, valence isomers of
benzene were prepared through elaborate organic synthe-
ses,[3–6] while hypercoordinated carbon compounds entered
the stage through the pioneering work of Olah on superacids
and non-classical cations.[7, 8]
The bonding situation in protonated methane (CH5+),
which is the most prominent representative of pentacoordi-
nated carbon, is best described as a 3-center 2-electron bond
between H2 and CH3+, but its isolation in bulk is elusive. The
replacement of hydrogen with organogold species lead to the
isolation of penta- and hexacoordinated methanium salts by
Schmidbaur. These carbido clusters, [(Ph3PAu)5C]+ and
[(Ph3PAu)6C]2+, are significantly stabilized by aurophilic
interactions.[9, 10] Recently, a related structural motive has
been identified in the iron-molybdenum nitrogenase cofactor,
which contains hexacoordinated C4 .[11] Taking a completely
[*] M. Sc. M. Malischewski, Prof. Dr. K. Seppelt
Freie Universitt Berlin
Institut fr Chemie und Biochemie—Anorganische Chemie
Fabeckstraße 34–36, 14195 Berlin (Germany)
E-mail: moritz.malischewski@fu-berlin.de
Supporting information (including experimental details, NMR spec-
tra, crystallographic data and information on the DFT calculations)
and the ORCID identification number(s) for the author(s) of this
article can be found under http://dx.doi.org/10.1002/anie.
201608795.
Angew. Chem. Int. Ed. 2016, 55, 1 – 4  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemie
International Edition: DOI: 10.1002/anie.201608795
German Edition: DOI: 10.1002/ange.201608795
different approach, Akiba and co-workers prepared formally
hypercoordinated organic species through special ligand
design, where an electrophilic carbon atom is intramolecu-
larly coordinated by two/four neighboring methoxy groups.
The C O distances are in the range of 2.43(1)–2.45(1)  and
2.641(5)–2.750(5) , respectively,[12, 13] thus indicating only
weak interactions. In stark contrast, hypercoordinated carbon
with much shorter bonds can be found in carboranes.
Nevertheless, these common structural motives of boron
chemistry are only subtly changed by replacing boron with an
isolobal carbon fragment. Surprisingly, even hexagonal-
planar carbon has been considered viable (based on theoret-
ical calculations by Exner and Schleyer) in boron compounds,
for example, in CB62 .[14]
Recently, the isolation of the non-classical norbornyl
cation and its crystal structure analysis was achieved by
Scholz et al.[15] In this species, a C C double bond (bond
length of 1.39 ) interacts with a carbocationic methylene
group at a distance of 1.80 , which can be rationalized as a 3-
center 2-electron bond. These results encouraged us to
attempt the isolation of C6(CH3)62+, where the hexacoordi-
nated carbon is exclusively bound to carbon atoms.
In analogy to electron-deficient boron clusters, the Wade
rules predict a pentagonal-pyramidal geometry (nido cluster)
for C6H62+. In 2014, the group of Roithova detected this
species after double ionization in the gas phase by infrared
predissociation spectroscopy at temperatures below 4 K, in
addition to an isomeric, strongly deformed six-membered ring
species.[16] Even though these results make it appear that the
isolation of pentagonal-pyramidal carbocations is elusive, the
stability of such a species can be increased by replacing the
hydrogen atoms by more electron-donating substituents.
Particularly noteworthy is Hogeveens preparation of the
hexamethylbenzene dication C6(CH3)62+ under superacidic
conditions in 1973, for which he assigned a pentagonal-
pyramidal structure based on NMR spectroscopy and reac-
tivity studies.[17–21] Herein we report the crystal structure of
C6(CH3)62+ (SbF6 )2·HSO3F, which revealed a non-classical
structure for this labile species (Figure 1).
Attempts to oxidize hexamethylbenzene to C6(CH3)62+
with powerful oxidants, such as SbF5/AsF5 in SO2 or O2+ in
anhydrous HF, failed, while treatment of hexamethyl-sub-
stituted Dewar benzene[22] with HF/AsF5 or HF/SbF5 lead to
the isolation of C6(CH3)6H+ As2F11 and C6(CH3)6H+ Sb2F11
(see the Supporting Information). This cation had already
been observed by Olah in 1968 by NMR,[23] and later
a disordered X-ray structure was published by Laube.[24]
Ultimately, a different approach lead to success: C6(CH3)62+
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Figure 1. Molecular structure of C6(CH3)62+ in C6(CH3)62+
(SbF6 )2·HSO3F, ellipsoids are shown at 50 % probability, C grey,
H white; counteranions and co-crystallized HSO3F omitted for clarity.
Figure 2. Preparation of C6(CH3)6H+ As2F11 /Sb2F11 and C6(CH3)62+
(SbF6 )2.
is best prepared by careful dissolution of hexamethyl Dewar
benzene epoxide[25] in magic acid (HSO3F/excess SbF5) and
crystallized by addition of an excess of anhydrous HF at low
temperature (Figure 2). Under superacidic conditions, O2 is
formally abstracted to generate C6(CH3)62+. When using
excess SbF5, the dication is quite stable in solution at low
temperatures (storage at 78 8C for days gives no indication
of decomposition). The solid crystalline material is very
unstable once the solution is decanted off and easily decom-
poses, however single crystals could be handled in a cold
nitrogen stream.
The compound crystallizes in the triclinic space group P1,
with one molecule of HSO3F incorporated in the asymmetric
unit.[28] Due to the excellent data quality (R1 = 1.8 %), the
position of all of the hydrogen atoms could be refined. The C
C bond lengths are in the range of 1.439(3)–1.445(2)  for the
bonds within the five-membered ring, 1.479(3)–1.489(3)  for
the C CH3 bonds, and 1.694(2)–1.715(3)  for the bonds to
the top of the pyramid. These values are very similar to those
obtained by DFT calculations (using B3LYP/def2-TZVP).
The pyramid height (derived from the crystal structure) is
about 1.18 , while it is noticeable that the basal methyl
groups are slightly bent upwards. The majority of the hydro-
gen atoms are involved in hydrogen bonding to surrounding
SbF6 anions.
The bonding situation in C6(CH3)62+ can be rationalized
by simple electron counting. The pentagonal-pyramidal
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species C6(CH3)62+ is formally an adduct of the pentamethyl-
cyclopentadienylium cation C5(CH3)5+ (which provides 4
electrons) and the 1-ethylium-1-ylidene cation CH3C+
(which provides 2 electrons), thereby giving 4n + 2 interstitial
electrons.[26] Alternatively, cluster-electron counting accord-
ing to the Wade rules yields 16 electrons, from which 10
electrons are subtracted for the formation of the five-
membered ring. Consequently, the interaction between the
apical carbon and the five-membered ring is formed by six
electrons, which is also confirmed by NBO calculations.
Additionally, Wiberg bond indices of ca. 0.54 for the
pyramidal C C bonds indicate a bond order of significantly
below 1, while the sum of all Wiberg bond indices per atom
does not exceed 4, so the octet rule is not violated for the
hexacoordinated carbon atom.
The calculated energetic sequence of C6(CH3)62+ isomers
differs depending on whether DFT or MP2 calculations are
used. The pentagonal-pyramidal structure of C6(CH3)62+ is
favored at the MP2/cc-pVTZ level (Figure 3), while DFT
Figure 3. Calculated relative energies of C6(CH3)62+ isomers. Structure
optimization: B3LYP/def2TZVP; single-point energies: MP2/cc-PVTZ.
calculations (B3LYP/def2TZVP) suggest that six-membered
ring species (in either singlet or triplet state) are energetically
favored (see Table S5 in the Supporting Information). Never-
theless, the formation of pentagonal-pyramidal C6(CH3)62+
can be additionally explained by the reaction mechanism (see
Figure S9).
C6(CH3)62+ gives two signals in the 1H NMR at 60 8C,
one at 2.51 ppm corresponds to the five basal methyl groups,
while the peak at 1.85 ppm corresponds to the apical methyl
group. The 13C spectrum exhibits four signals. A singlet at
8.5 ppm can be observed for the basal methyl groups, while
the singlet of the carbon atoms of the five-membered ring
appears at 125.3 ppm. The upfield-shifted resonance at
21.0 ppm is typical for a carbocation with a high coordination
number and can be assigned to the top of the pyramid, while
the signal at 4.5 ppm belongs to the attached methyl group.
The very unusual (in a dication) slightly negative chemical
shift of the apical methyl group in the 13C NMR prompted us
to apply Schleyers nucleus-independent chemical shift
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(NICS) criterion[27] to investigate the magnetic shielding in
C6(CH3)62+. The values of NICS(0.5) 40.553 and NICS(1)
41.004 inside the pyramidal cone are larger than NICS-
( 0.5) 13.878 and NICS( 1) 9.262, but they all indicate
the presence of induced diatropic ring currents, which is
typical for a three-dimensional aromatic system.
In summary, the non-classical C6(CH3)62+ dication was
prepared as the SbF6 salt through the dissolution of
hexamethyl Dewar benzene epoxide in magic acid. The
crystal structure of C6(CH3)62+ (SbF6 )2·HSO3F is the first
representative of a pentagonal-pyramidal benzene dication
and its hexacoordinated carbon that is only bound to carbon
atoms is without precedent.
Acknowledgements
This work was supported by the Free University Berlin,
Verband der Chemischen Industrie (VCI) and Deutsche
Forschungsgemeinschaft (GRK 1582 (Fluorine as a Key
Element)). Computing time was made available by High-
Performance Computing at ZEDAT/FU Berlin.
Keywords: carbocations · electron-deficient compounds ·
hypercoordination · oxidation · superacids
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[28] CCDC 1496329 [C12H19As2F11], 1496330 [C12H18(SbF6)2·HSO3F],
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charge from The Cambridge Crystallographic Data Centre.
Received: September 8, 2016
Revised: October 16, 2016
Published online: && &&, &&&&
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Communications
Carbocations Hexacoordinated carbon can be observed
the crystal structure of the non-classical
M. Malischewski,* dication C6(CH3)62+ (SbF6 )2·HSO3F.
K. Seppelt &&&&—&&&& Pentagonal-pyramidal C6(CH3)62+ was
obtained through the dissolution of hex-
Crystal Structure Determination of the amethyl Dewar benzene epoxide in
Pentagonal-Pyramidal HSO3F/SbF5.
Hexamethylbenzene Dication C6(CH3)62+

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