The history of aromatic chemistry is dominated by the concept
of planar ring systems containing 4
n + 2 conjugated
electrons, the so-called Hückel rule of aromaticity.
Heilbronner
1
in 1964 was the first to
suggest that applying a Möbius twist to the ring would create an
aromatic species if 4
n electrons were conjugated. The
Möbius concept has been widely applied to considering the aromaticity
of pericyclic transition
2
states, but only
recently have candidates for stable Möbius aromatics been suggested.
Schleyer and coworkers have reported that a Möbius twisted
conformation of the 4
n system
C
9H
9+ is aromatic
3
on the basis of calculated nucleus independent
chemical shifts (NICS),
2
a technique which
appears reliable and useful at quantifying aromaticity. We recently
reported calculations on two conformations of [16]annulene,
4
one being conventionally antiaromatic, but the
other having a pronounced Möbius-like twist not associated with any
particular region of the ring. This isomer exhibited a NICS value
consistent with mild aromaticity rather than antiaromaticity. Here we
suggest further candidates for consideration as Möbius aromatics.
Our initial focus was on the chiral species cycloheptatetraene
5. The presence of a C
C
C substructure in the
7-membered ring reduces the dihedral angle between the 1,3 allene
substituents from 90 to 47–50°, which has the effect of breaking
the degeneracy of the two highest occupied allene orbitals (Fig. 1; see
ESI
†
). Interaction of both resulting
orbitals with the remaining ring
orbitals would create a similar
Möbius topology to that envisaged by Heilbronner, the specific case of
5 resulting in what could be termed a [7]Möbius annulene. A
NICS calculation (
6.5 ppm,
Table
1) establishes that this orbital interaction results in a mildly
aromatic system, being rather less so than benzene itself (NICS
10
ppm). NICS calculations on benzannulated derivatives of
5 were
reported
5
but the aromaticity of the
allene-derived ring was not discussed. The
40° distortion at the
allene unit in
5 is clearly destabilising, since the species
is
isolable only at low temperatures, dimerising at higher
temperatures
via a
2 +
2
cycloaddition (a process known to be inhibited by bulky groups at the 1,3
positions
6
). The calculated bond lengths for
5 also show some alternation, indicative of a reactive species
(
Fig. 2). The HOMO and HOMO
1 AM1
orbits computed for
5 are both symmetric with respect to
C2 axis and derive from the twisted allene system, but
are now delocalised over the entire ring, and show Möbius topology
(
Fig. 2). Heilbronner predicted the HOMO for
a pure Möbius aromatic would exhibit degeneracy,
1
but purely in a Hückel MO context. No
degenerate representations in
C2 symmetry are necessary
in
5, although we do note that the energy difference between HOMO
and HOMO
1 (1.6eV/AM1) is less than that for allene at this twist
angle (2.2 eV, Fig. 1
†
).
Table 1
Energies [kcal mol
1 for AM1,
Eh
(Hartree) for RHF/6-31G(d)] and NICS values (ppm) for the ground state
structures
|
Fig. 2
Calculated geometry (a) (Å, AM1 (RHF-6-31G(d)) [B3LYP/6-31G(d)]
and form of the AM1 HOMO (b) and HOMO 1 (c) orbitals for
5. |
As a ligand,
5 is unusual in binding metals to both
faces
concurrently (
e.g.7),
7
but this is perhaps not unexpected if one
considers it having only a single
-face! We also estimate one
consequence of
5 (and its metal complexes) being chiral. Thus a
typical model chiral auxilliary (
e.g. R = CHClI or R =
camphorsultamil
8
) results in
diastereoisomers differing in energy by about 0.4–0.6 kcal
mol
1 (AM1), a relatively small discrimination, but
possibly one capable of being increased by suitable design.
5
interconverts with its mirror image
via the Hückel
4
n + 2
aromatic
6 (cycloheptatrienylidene),
9
which at the correlated level (CASPT2) has
recently been shown to be the transition state for this process (barrier
20 kcal mol
1).
Elaborating the theme of substituting C
C
C for C
C
(
Table 1) we noted that the small ring
systems
1 and
2 would be classified as antiaromatic;
2 as a conventional 4
antiaromatic Hückel system with a
triplet ground state and
1 as a 4
n + 2 6
Möbius
antiaromatic system.
1 appears not to exist as a minimum at the
ab initio RHF level, whilst singlet
2 reveals an
antiaromatic (positive) NICS value. No minimum for the anion
3
could be located for this putative 8
Möbius aromatic, all
optimisations resulting in the aromatic Hückel valence bond isomer
4, probably because twisting the allene component in
3 to
accommodate a 6-membered ring requires too much energy. This is a lesser
problem in the larger ring monocation
8, which appears to be a
C2 symmetric 8
Möbius system exhibiting NICS
aromaticity, as is the 8
dication
9. The singlet neutral form
of
9/11 as an antiaromatic 4
n + 2 10
annulene
distorts to remove all symmetry and localise the bonds, whereas the triplet
neutral
9/
10 retains
C2 symmetry as
might be expected of a 4
n + 2 excited state Möbius aromatic,
although the NICS value shows only slight aromaticity (
1.3
ppm).
10
Chiral 12
monoanion
10
and the dianion
11 also show aromatic NICS values and have
non-planar twisted geometries (
Table 1).
Each ring of the chiral bicyclic analogue of naphthalene
12 shows
only modestly aromatic NICS values. In this instance, the carbene valence
bond isomer
13, a bridged [10] 4
n + 2 Hückel
aromatic annulene, is substantially lower in energy, making it unlikely
that
12 is a viable synthetic target. System
14 is
derived from the novel Hückel-aromatic S/N systems discovered by Rees
and Surtees.
11
As an 8
Möbius,
14 has an aromatic NICS value (
Table
1). The 12
system
15 has a much smaller NICS value,
which might be related to the larger dihedral angle at the allene termini
(75°,
Table 1) reducing the
Möbius like orbital mixing (
c.f. Fig. 1
†
). Our results do imply that optimum Möbius
aromaticity may be achieved at allene twists of
30–60°.
The presence of two or more allene-like chiral Möbius components
raises the possibility that these can oppose or cooperate. An even number
of the former becomes equivalent to Hückel; but if the latter the
topological implications become more complex. For
17 two
conformations can indeed be located, one with
CS
(Hückel) and the other with
C2 (Möbius)
symmetry, the latter being lower in energy and higher in aromaticity
(
Table 1). In the 10
Hückel
aromatic conformation of the alkyne
17, the triple bond appears to
act purely as a two electron contributor whereas in the
C2 form, a possible four-electron alkyne contribution
results in 12
Möbius aromaticity. The alkene analogue
18
has smaller NICS aromaticity values and relative energies, due in part to
the significant non-planarity of
18. More intriguingly the higher
aromaticity of
17 may be due to in-plane trannulene like
aromaticity.
12
The alkyne in
16
appears to act as a Möbius contributor, cooperating with the allene
component to give a modestly aromatic 12
system. The isomers
19 and
20 also have two conformations. Hückel
19 as an 8 or 12
4
n antiaromatic has the expected
positive NICS value, whilst
C2 symmetric
19 is
slightly Möbius aromatic. Compared to
19, isomers
20
show reversed NICS values (
Table 1), and
may be indicative of more complex topological contributions to the
aromaticity. A single Möbius component inserted into
e.g.
[14]trannulene
21 appears much less aromatic than the trannulene
itself (
Table 1), but it does conform to
a 4
n rather than a 4
n + 2 rule for aromaticity. Finally
we note that
C2 symmetric
22 has three allene
contributions and as a 12
system it would be expected to be Möbius
aromatic. Two isomers were identified, one with
C2 and
a lower energy and more aromatic form with
C3 symmetry
in which all three allene units cooperate.
We conclude that a diverse range of Möbius 4
n
aromatic systems can be constructed by using one or more twisted allene
fragments as an initiator. The origins of the Möbius and Hückel
contributions to the aromaticity and the nominal electron contributions
(4
nvs. 4
n + 2) of these systems may be quite
subtle. A dissection of these origins will be reported in a future
article.