DOI: 10.1002/chem.

201504744 Communication

& Organo-Main Group Derivatives

Stepwise Reduction of an a-Phosphonio–Carbocation to

a Crystalline Phosphorus Radical Cation and an Acridinyl–
Phosphorus Ylide
Todd W. Hudnall,*[a] Christopher L. Dorsey,[a] James S. Jones,[b] and FranÅois P. Gabbaı̈*[b]

Chem. Eur. J. 2016, 22, 2882 – 2886 2882 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communication

Abstract: We have synthesized the dicationic a-phospho-

nio–carbocation 12 + , which can be regarded as a two-
electron oxidized phosphorus ylide. Carbocation 12 + ex-
hibits two reversible reduction waves at ¢0.28 and
¢0.90 V (vs. Fc + /Fc) indicating that both the radical cation
1C + and the neural phosphorus ylide 1 can be generated.
Indeed, reduction of 12 + with Zn afforded 1C + as a dark
green solid that was characterized by XRD and EPR spec-
troscopy, and reduction with Mg(Ant)·(THF)3 gave 1, which
was characterized by 1H and 31P NMR spectroscopy. Com-
putational analyses reveal the stepwise population of
a C¢P p bonding orbital upon reduction of 12 + .
Scheme 1. Synthesis of compounds 12 + (OTf)2, 1C + (OTf) and 1. Conditions: i:
PPh3, TMSOTf, C6H5Cl, 25 8C; ii: Zn (excess), MeCN, 25 8C; iii: Mg(anthrace-
ne)·(THF)3, 1 equiv, THF, 25 8C.
Redox-active organic molecules that are stable in multiple oxi-
dation states are of potential interest for the development of
new materials for organic electronics and battery applica- dinium dication 12 + which could be easily obtained as a triflate
tions.[1] In this context, we have been interested in the funda- salt by reaction of 9-bromo-N-methylacridinium triflate with
mental chemistry of organo-main group derivatives that are Ph3P in PhCl in the presence of TMSOTf (Scheme 1). The bright
stable in at least two redox states. In an earlier study, we yellow salt 12 + (OTf)2 is soluble in polar solvents such as MeCN;
showed that a-borylated carbocations can be reduced by one it can be easily handled in air without noticeable decomposi-
or two electrons to afford the corresponding boryl radical or tion. Some of its salient physicochemical features include:
borataalkene, respectively.[2] In search of other main group a 31P NMR resonance at d = 20.78 ppm, a 1H NMR resonance at
platforms that could support analogous redox processes, we d = 5.07 ppm corresponding to the N-methyl group, a 13C NMR
have turned our attention toward a-phosphonio–carbocations resonance of the C9 carbon atom of the acridinium unit at d =
of type A2 + and their possible stepwise reduction into the cor- 142.85 ppm, and a molecular ion detected at m/z 227.58 amu
responding a-phosphonio–methyl radical cations AC + and by electrospray ionization mass spectrometry. This 12 + (OTf)2
phosphorus ylides A (Figure 1).[3] These studies were further has been structurally characterized (Figure 2, left). Inspection

Figure 1. Stepwise reduction of a-phosphonio–carbocations (A2 + ) to gener-

ate radical cations AC + and phosphorus ylides A.

stimulated by the realization that while the one-electron oxida-

tion of phosphorus ylides has been established in solution,[4]
their double oxidation into a-phosphonio–carbocations of
type A2 + has never been experimentally confirmed.[5]
It occurred to us that accessing a dication of type A2 + may
necessitate stabilization of the methylium moiety via electronic
effects. With this in mind, we targeted the a-phosphonio–acri-
[a] Prof. Dr. T. W. Hudnall, Dr. C. L. Dorsey
Department of Chemistry and Biochemistry
Texas State University
San Marcos, TX 78666 (USA)
E-mail: hudnall@txstate.edu
[b] J. S. Jones, Prof. Dr. F. P. Gabbaı̈
Department of Chemistry
Texas A&M University
College Station, TX 77843 (USA)
E-mail: francois@tamu.edu
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201504744.
Figure 2. Crystal structure (left, hydrogen atoms and counter anions are
omitted for clarity, ellipsoids set at 50 % probability) and LUMO (right, 0.04
isovalue) of 12 + .
of the molecular structure indicates that the P1¢C9 distance
(1.835(4) æ) is slightly elongated when compared to the P1¢CPh
bonds (av. 1.797 æ). This elongation can be assigned to electro-
static repulsion between the phosphonium center and the C9
methylium center. The acridinium moiety is nearly planar (C9
and N1 are displaced by less than 0.2 æ from the acridine
plane) owing to stabilization of the carbocationic center by the
aromatic p system. To better understand the bonding in this
dication, we optimized its structure (B3LYP/6-311 + + G(2d,p))[6]
and compared it to the computed structure of the monocation
triphenyl-9-acridinyl–phosphonium. These computational stud-
ies show that the P¢Cacr bond length increases from 1.848 to
1.893 æ upon methylation, thus supporting the presence of in-

Chem. Eur. J. 2016, 22, 2882 – 2886 www.chemeurj.org 2883 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

creased electrostatic repulsion in the dication. These studies
also indicated that the LUMO of 12 + is localized on the methyl-
ium carbon atom (Figure 2, right), pointing to the relevance of
resonance form B (Scheme 1).
With this compound in hand, we decided to probe its redox
properties using cyclic voltammetry. In MeCN, 12 + exhibited
one reversible and one irreversible wave (see the Supporting
Information); however when a MeCN solution of 12 + was in-
jected into THF, two reversible reduction waves were observed
at ¢0.28 and ¢0.90 V (vs. Fc/Fc + , Figure 3, top) in agreement
Figure 3. Top: CV of 12 + obtained by injecting 10 mL of a 0.2 m solution of
the dication in MeCN into 3 mL of THF; bottom: CV of 1 generated in situ in
THF, (0.1 m TBAPF6, 0.1 mV s¢1, sweep direction is indicated by the arrow).
with the elelctrophilic nature of the dication. The detection of
these two waves suggested that both the radical cation 1C +
and phosphorus ylide 1 may be sufficiently stable to isolate. To
verify this assumption, 12 + was reduced with an excess of Zn
in MeCN to produce a dark green suspension of 1C + . EPR spec-
troscopy carried out on this solution after filtering out precipi-
tated magnesium salts allowed the detection of a signal which
is split into a doublet by a 31P hyperfine coupling constant of
18 G (Figure 4). This hyperfine coupling constant can be com-
pared to the value of 26.3 G reported for [Ph3PCPh2]C + .[4] The
fine structure of the spectrum could be further simulated
using the hyperfine coupling constants shown in Figure 4,
which are typical of N-methyl–acridinyl radicals.[7]
Encouraged by the stability of these solutions, we attempted
isolation of the radical cation. Compound 1C + could be isolated
as a green solid upon workup from reduction in MeCN, and
dark green single crystals of were obtained by slow vapor dif-
fusion of Et2O into a solution of MeCN saturated with the radi-
Figure 4. Experimental and simulated EPR spectra of 1C + (left) and hyperfine
coupling constants used for the simulation (right).
Chem. Eur. J. 2016, 22, 2882 – 2886 www.chemeurj.org
Communication
cal allowing structural elucidation. The structure of 1C + OTf
shows that the P1¢C9 bond (1.773(4) æ) is shorter than the
corresponding linkage in 12 + (Figure 5, left). This shortening is
assigned to a decrease in electrostatic repulsion as well as the
onset of P¢C p-bonding. We also observed a puckering of the
central C5N ring of the acridine moiety, with the C9 and N1
atoms displaced by 0.26 and 0.21 æ, respectively, above the
C10-C11-C12-C13 plane.[8]
Figure 5. Crystal structure (left, hydrogen atoms and counter anion are omit-
ted for clarity, ellipsoids set at 50 % probability) and SOMO (right, 0.04 isoval-
ue) of 1C + .
To further characterize the P1¢C9 bonding, we optimized
the geometry of this radical using DFT methods (UB3LYP/6-
311 + + G(2d,p))[6] and obtained a structure that closely
matched that determined experimentally. The SOMO of 1C +
shows a large contribution from the p orbital of the former
methylium center, C9, as can be expected (Figure 5, right), and
closer inspection revealed minor contribution from the P1¢C15
s* orbital. Moreover, the hyperfine coupling constants from
the acridine–hydrogen atoms underscore the effective delocali-
zation of the spin density onto the acridinyl fragment. In
agreement with this view, we note that the P1¢C15 bond is
oriented orthogonally to the P1-C9-C10-C12 plane in the crys-
tal structure with a torsion angle of 90.98, consistent with don-
ation from the unpaired electron on C9 into the P1¢C15 anti-
bonding orbital. NBO analysis revealed that the shortening of
the P1¢C9 bond on going from 12 + to 1C + can be attributed
to a donor–acceptor p-backbonding interaction from the radi-
cal on C9 into the P1¢C15 s* orbital.
We next focused our efforts toward the double reduction of
12 + to afford the phosphorus ylide 1. While many reducing
agents such as Na/Hg and KC8 were found to completely
reduce 12 + , decomposition of the ylide was prevalent, and we
found the cleanest reduction to take place in THF using
1 equiv of Mg(Ant)·(THF)3 (Scheme 1, Ant = C14H10). Indeed,
slow drop-wise addition of a THF solution of Mg(Ant)·(THF)3 to
a suspension of 12 + (OTf)2 resulted in the formation of a dark
red solution. Importantly, the solvent must be removed from
the reaction mixture, and the ylide extracted using aromatic
hydrocarbons, within 30 min of adding the reducing agent to
prevent decomposition. Extraction of the crude product with
benzene afforded a dark red suspension which was filtered
over Celite in a glove box followed by solvent removal to
afford a mixture of ylide 1, anthracene, and PPh3 (presumably
due to minor decomposition). Despite numerous attempts, we
2884 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

failed to isolate the ylide, including reactions carried out at low
temperature.
Despite the mixture of products, ylide 1 could be easily char-
acterized by 1H and 31P NMR spectroscopy (C6D6, see Figure 6,
Figure 6. Aromatic region of the 1H NMR spectrum of the reaction of 12 +
with Mg(Ant)·(THF)3 (left, o = anthracene, x = Ph3P) and the HOMO of 1 (0.04
isovalue).
left). The phosphorus signal for 1 was observed upfield relative
to that of 12 + at d = 3.68 ppm and is both consistent with
a loss of cationic character, and with what has been observed
for Ph3P=CPh2 (d = 6.6 ppm, THF). In agreement with a loss of
cationic character the N-methyl substituent in 1 was observed
at d = 2.98 ppm, more than 2 ppm upfield compared to that of
the dication 12 + . Despite our best efforts, we were unable to
obtain 13C NMR data or single crystals to further characterize 1.
In our hands, it was found that 1 was extremely fragile and
would decompose in solution within a day. This is not surpris-
ing given that two-electron reduction of the methylium center
in 12 + would result in a formally antiaromatic ylide. To verify
that 12 + can be regarded as the doubly oxidized form of ylide
1, we obtained the CV of 1 in THF (Figure 4, bottom), which re-
vealed two reversible oxidation waves (E1/2 = ¢0.89 and
¢0.29 V, vs. Fc/Fc + ) that were nearly identical to those ob-
served in the CV of 12 + .
To determine if compound 1 was indeed characteristic of
a phosphorus ylide, we performed DFT calculations (B3LYP/6-
311 + + G(2d,p)),[6] which revealed that the HOMO of 1 is domi-
nated by a p orbital between the P1 and C9 centers (Figure 6,
right). To gain further insight into the changes in P¢C bonding
upon stepwise reduction, compounds 12 + , 1C + , and 1 were
subjected to Pipek–Mezey localization (PML) analysis[9] at their
DFT-optimized geometries. In accordance with the expected
population of the P¢C p orbital, PML orbitals corresponding to
the P¢C p bond were found for 1C + and 1 (Figure 7). The local-
ized p orbitals in both cases show major contributions from
the ipso-acridine carbons (62.4 % for 1C + , 46.8 % for 1) and
minor contributions from the phosphorus centers (8.9 % for 1C +
, 17.3 % for 1), consistent with the highly polar nature of the
P¢C bond. Significant additional contributions to the localized
p orbitals also come from ipso-carbons of the phosphorus-
bound phenyl substituents (see the Supporting Information).
Chem. Eur. J. 2016, 22, 2882 – 2886 www.chemeurj.org
Communication
Figure 7. PML orbitals corresponding to P¢C p bonds in 1C + (left) and
1 (right) (Isovalue = 0.05). Hydrogen atoms are omitted for clarity.
As the establishment of the P¢C p system can alternatively be
explained in the context of alleviation of the anti-aromatic
character of the acridinyl fragment through interaction with P¢
C s* orbitals, the contribution of these carbon atoms to the lo-
calized orbitals is noteworthy. No localized P¢C orbitals with p
symmetry were found in the case of 12 + , in line with the ex-
pected vacancy of the P¢C p orbital in this compound. To pro-
vide comparison of 1 with model ylides, Ph3P=CPh2 and Ph3P=
CH2 were subjected to optimization by DFT methods, followed
by PML analysis. Similar to the PML orbital corresponding to
the P¢C p bond in 1, the atomic contributions to the PML or-
bitals for the P¢C p bonds in Ph3P=CPh2 (46 % C, 17.4 % P) and
Ph3P=CH2 (49.6 % C, 21.1 % P) are dominated by the carbon
atom involved in p bonding, again illustrating the polar nature
of the P¢C double bond.
To complement the PML analysis, the DFT-optimized struc-
tures of compounds 12 + , 1C + , and 1 were next subjected Quan-
tum Theory of Atoms in Molecules (QTAIM)[10] analysis. Relevant
data derived from the electron density distribution function
(1(r)) at the bond critical points (BCP) of the phosphorus–acri-
dinium (P¢Ca) linkages in 12 + , 1C + , and 1 are presented in
Table 1. Additional parameters derived from AIM analyses are
Table 1. Selected features of 1(r) at the phosphorus–acridinium ipso-
carbon bond critical points in 12 + , 1C + , and 1.
H
Compound 1BCP [e æ¢3] e d(P,C) 1(r) [e æ¢1]
P\C
2+
1 1.027 0.05 0.80 2.05
1C + 1.174 0.15 0.88 2.48
1 1.292 0.39 1.01 3.12
Ph3P=Ph2 1.290 0.40 1.03 N/A[a]
Ph3P=CH2 1.346 0.42 1.12 2.81
[a] Due to the necessity to integrate Hthe relevant atomic basins using the
‘Promega’ algorithm in AIMAll, the P\C1(r) value could not be deter-
mined.
presented in the Supporting Information. Inspection of the
values of 1(r) at the P¢Ca BCPs finds that they increase across
the series in line with the expected increase in P¢Ca bond
order. Further corroborating the increase in P¢Ca bond order
across the series are the trends in the delocalization indices
(d(P,Ca)),[11] which correspond to the number of electron pairs
delocalized between the two atoms and the values of the inte-
2885 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

H
grals of 1(r) across the P¢Ca interatomic surfaces ( P\Ca1(r)).
While the values of d(P,Ca) increase across the series in accord-
ance with the increasing formal P¢Ca bond order, the d(P,Ca)
value of 1.01 obtained for 1 is considerably less than expected
for a true double bond. The diminished d(P,Ca) values in this
series, however, may be explained by the strongly polarized
nature of the P¢Ca bond which results in reduced covalency.
The ellipticity parameter (e), which measures the distortion of
electron density accumulation from cylindrical symmetry at
a BCP, can also provide an indication of p character within
a bond. The ellipticity value of 0.05 at the P¢Ca BCP in 12 + in-
dicates little distortion from cylindrical symmetry. In contrast to
12 + , the P¢Ca BCPs in 1C + and 1 feature elevated ellipticity
values of 0.15 and 0.39, respectively. The heightened ellipticity
values at the P¢Ca BCPs in 1C + and 1 signify a distortion of the
P¢Ca bond from cylindrical symmetry due to the population of
the P¢Ca p orbital. QTAIM parameters calculated for the DFT-
optimized structures of the model ylides Ph3P=Ph2 and Ph3P=
CH2 closely match those found for 1 suggesting that the P¢C
p bonds in these species are electronically similar.
In summary, we have demonstrated conclusively that a-
phosphonio–carbocations (12 + ), the two-electron oxidized
phosphorus ylides, can be prepared as air-stable compounds.
Additionally, 12 + can be chemically reduced by one or two
electrons to afford a stable a-phosphonio–methyl radical
cation 1C + or a fragile antiaromatic phosphorus ylide 1. Com-
putational and crystallographic data reveal that stepwise popu-
lation of a C¢P p-bonding orbital upon reduction of 12 + . Col-
lectively, these results detail the first system in which all three
oxidation states of phosphorus ylide-derived compounds could
be isolated and characterized.
Acknowledgements
The authors would like to acknowledge the National Science
Foundation for grants CHE-1362140 (T.W.H.), CHE-0821254 and
CHE-0946998 (M.R.I.), CHE-1300371 (F.P.G.), the American
Chemical Society-PRF for grant 54584-UR3 (T.W.H.), the Welch
Foundation for grant A-1423 (F.P.G.), Texas A&M University (A.E.
Martell Chair, F.P.G.), and the Laboratory for Molecular Simula-
tion at Texas A&M University (software and computation re-
sources).
Chem. Eur. J. 2016, 22, 2882 – 2886 www.chemeurj.org 2886
Communication
Keywords: carbocation · main group elements · phosphorus ·
radical · ylide
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Received: November 25, 2015
Published online on January 7, 2016
Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim