Communications
4,4’-bipyridylidene core bearing two benzannulated s4-l4-
[1,3,2]diazaphosphole fragments at each terminus; each
phosphorus atom has a distorted tetrahedral environment.
Both the 4,4’-bipyridylidene unit and the diazaphosphole
rings show substantially localized bonding patterns and are
planar within Æ 0.04 and Æ 0.03 ꢀ, respectively, with an angle
of 6.58 between the two planes of the ring systems. The phenyl
À
rings are inclined to the bipyridylidene core by 388. The C(4)
C(4’) distance, 1.394(5) ꢀ, is consistent with a pseudo-
À
quinoidal structure and compares well with the central C C
distance of 1.381(3) ꢀ reported for the two-electron reduced
bis(trimethylsilyl)dihydro-4,4’-bipyridine, (cf. localized 4,4’-
bipyridine, 1.486 ꢀ).[8]
X-Ray analysis of a selection of individual crystals
revealed each to be trans-2. However, the 31P NMR spectrum
(CD2Cl2) of this small sample of crystalline material consis-
tently showed the presence of both cis and trans isomers in an
approximately 1:1 ratio, with the exact proportions being
sample-dependent. Since the two isomers of 2 do not
interconvert in solution (see above), this suggests that cis-2
is present in amorphous form alongside crystalline trans-2.
Although repeated attempts were made to separate cis-/trans-
2 by fractional crystallization and by chromatography, these
proved unsuccessful.[6]
The mechanism for the formation of diphosphonium salt 2
from reaction of [(iPr2N)2P][OTf] with 1o/1c is not readily
apparent. Despite extensive efforts no phosphorus-containing
by-products could be detected in the reaction mixture, prior
to purification, by 31P NMR spectroscopy.[6] Most likely the
unaccounted for material is lost in the form of intractable
oligomeric products that are removed during the purification
Scheme 3. Proposed mechanisms for the formation of 2 from 1.
coupling followed by double deprotonation (pathway A) or,
reaction with a second equivalent of 1o/1c generating [2]+,
which is subject to elimination of H+ and oxidation to yield 2
(pathway B). Both pathways are supported by the observed
formation of sub-stoichiometric quantities of [iPr2NH2][OTf]
resulting from the generation of acid following reaction of 1o/
1c with either [(iPr2N)2P][OTf] or [Cp2Fe][OTf].[6] Further-
more, both paths A and B involve singly-bonded biaryl
species consistent with the formation of a 1:1 mixture of cis-/
trans-2; this is supported by a DFT study (B3LYP/6-31G*),
which revealed that trans-2 is only 1.8 kJmolÀ1 lower in
energy than cis-2.[6]
From a structural standpoint, the dihydro-4,4’-bipyridine
core of the dicationic component of 2 resembles that of the
doubly-reduced N,N’-dimethyl-4,4’-bipyridinium dication,
known commonly as “reduced viologen”, MV0.[16] Initially
developed as herbicides, the viologens constitute a well-
known class of redox-active compound, which give rise to
intensely colored, stable radical monocations.[16] The exten-
sive electrochromic behavior reported for the viologens has
led to their use in a range of applications including as electron
relays, redox mediators in catalytic cycles, and molecular-
scale devices.[17–19] Thus, it was of interest to further probe the
electronic character of dication 2 and the extent of its
similarity with MV0.
of 2, something consistent with the observation of [iPr2NH2]-
[6]
À
[OTf] formed by P N bond cleavage (see below).
Elucidation of the mechanistic pathway by which 2 is
formed is further complicated by the ambiphilic nature of the
phosphenium ion.[2] However, a hydride abstraction process
can be ruled out since: 1) no (iPr2N)2PH[9] was detectable
from the reaction of [(iPr2N)2P][OTf] with 1o/1c, and 2) no
reaction takes place on treating 1o/1c with an equimolar
quantity of the trityl salt [Ph3C][B(C6F5)4].[6] Thus, in order to
reduce the complexity of the system, an alternative cationic
Lewis acid/oxidant, namely a ferrocenium salt, was employed.
Indeed, treatment of a CH2Cl2 solution of 1o/1c with one
equivalent of [Cp2Fe][OTf][10] (Cp = cyclopentadienyl)
resulted in the near-instantaneous formation of a blue-green
solution from which cis-/trans-2 (1:1) was isolated in 39%
yield following purification.[6]
Together, these observations suggest that the formation of
2 from 1o/1c involves a radical-based process, which may be
regarded as a variant of the intermolecular Scholl reaction
(i.e. a Friedel–Crafts aryl coupling).[11] Although the mecha-
nism for this type of transformation is not well-established,
the intermediacy of a radical cation has been implicated.[12–14]
Indeed, such a process was invoked to account for the
formation of N,N’-disilyldihydropyridines through silylation
of pyridine in the presence of Pd/C.[15] Consequently, two
reaction pathways for the formation of 2 are proposed here
(Scheme 3). Both depend on the initial formation of the
radical cation [1]C, which then undergoes either a two-radical
A computational study using time-dependent density
functional theory (TD-DFT) methods (B3LYP/6-31G*)
gave an optimized structure for the dication of 2 that was in
excellent agreement with that obtained by X-ray crystallog-
raphy.[6,20] The computed absorption maxima (lmax = 761 nm,
e = 20000 dm3 molÀ1 cmÀ1) correspond well with those deter-
mined experimentally (see below), with the band at 761 nm
being comprised largely of a transition from the HOMO to
the LUMO (73%). As expected, the computed HOMO and
LUMO for 2 extend across the whole of the dication and are
consistent with a quinoidal-type structure, although only a
small orbital component is located at the two formally
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ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2009, 48, 9109 –9113