ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 1, pp. 78–87. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.V. Shaturin, V.S. Senchurin, O.K. Shaturina, E.A. Boyarkina, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 1,
pp. 80–89.
Tetraphenylphosphonium Carboxylates and Sulfonates.
Synthesis and Structure
V. V. Shaturin, V. S. Senchurin, O. K. Shaturina, and E. A. Boyarkina
Blagoveshchensk State Pedagogical University,
ul. Lenina 104, Blagoveshchensk, 675000 Russia
e-mail: vvsharutin@rambler.ru
Received May 20, 2008
Abstract―The reaction of the pentaphenyphosphorus solvate Ph5P·1/2PhH (I) with carboxylic and sulfonic
acids was used to synthesize tetraphenylphosphonium carboxylates Ph4POC(O)R, R = C6H4(2-OH) (II), C6H4
(2-СОOH) (III), Н (IV), Me (V), CCl3 (VI), Ph (VII), PhCH=CH (VIII), CH2CH2C(О)ОН (IX), CH=CHС(O)
ОН (X), and CH2С(О)ОН (XI) and tetraphenylphosphonium sulfonates Ph4POSO2Ar, Ar = Ph (XII), C6H4Me-
4 (XIII), and C6H3(-СОOH)(4-OH) (XIV). Compound XII was also prepared from compound I and SO3 in
benzene. According to X-ray diffraction data, the crystals of I contain two types of crystallographically
independent molecules with a slightly distorted trigonal-bipyramidal configuration [Ia, CaxPCax 178.44(8)°, P–
Cax 1.985(2), 1.987(2) Å, P–Ceq 1.854(2), 1.846(2), 1.840(2) Å; Ib, CaxPCax 178.45(9)°, P–Cax 1.980(2), 1.975
(2) Å, P–Ceq 1.840(2), 1.846(2), 1.854(2) Å]. In the cations of compounds II, III and XIV, the coordination of
the phosphorus atom is tetrahedral [CPC angle: II, 106.2(2)–111.6(1)°; III, 104.01(6)–113.03(6)°; XIV, 107.54
(6)–112.79(6)°]; the anions contain intramolecular O–H···O hydrogen bonds between the hydroxyl hydrogen
atom and carboxyl oxygen atom (II, 1.34; III, 1.23; and XIV, 1.83 Å).
DOI: 10.1134/S1070363209010125
Pentaphenylphosphorus is known to crystallize
from organic solutions as solvates, e.g., Ph5P·1/2cyclo-
C6H12 [1].
120.24(9)° (Ib). In agreement with the valence-shell
electron-pair repulsion (VSEPR) theory, the axial P–
Cax distances [1.985(2), 1.987(2) Å (Ia) and 1.975(2),
1.980(2) Å (Ib)] are longer than equatorial P–Ceq
[1.840(2), 1.848(2), 1.854(2) Å (Ia) and 1.840(2),
1.846(2), 1.854(2) Å (Ib)].
We synthesized pentaphenylphosphorus from tetra-
phenylphosphonium iodide and phenyllithium and
extracted it from the reaction mixture with benzene,
where its solubility is higher than in cyclohexane.
After filtration and removal of the solvent we obtained
colorless crystals which, by X-ray diffraction data, are
pentaphenylphosphorus solvate with benzene, Ph5P·
1/2PhH (I) (Fig. 1). In the crystals of I, there are two
types of crystallographically independent pentaphenyl-
phosphorus molecules with a trigonal-bipyramidal
central atom. The slight coordination distortion is
evidenced by the values of the CaxPCax axial angles
[178.44(8)° and 178.45(9)° in Ia and Ib, respectively]
and bond angles CaxPCeq between the axial and equa-
torial substituents [86.53(8)°–92.44(8)° and 86.34(8)°–
92.68(8)° in Ia and Ib, respectively], that are close to
the theoretical values 180° and 90°. The sums of the
equatorial bond angles are 359.99(9)° (Ia) and 359.91°
(Ib); therewith, the individual CeqPCeq angles span the
ranges 118.73(9)–120.73(9)° (Ia) and 119.67(9)°–
The overall conformation of the phenyl rings in the
equatorial plane in both Ia and Ib is not propeller. The
C
111–C116 and C121–C126 phenyl rings in Ia are turned
around the equatorial bonds by large torsion angles,
while the C141–C146 plane of the third ring practically
coincides with the equatorial plane; therewith, one of
the rings (C121–C126) is turned to a direction opposite to
that of the other two rings. The corresponding torsion
angles are as follows: C131P1C111C116 –39.44°;
C
151P1C111C112 –41.98°; C131P1C121C126
55.74°;
C151P1C121C122 58.11°; C131P1C141C166 –93.45°; and
151P1C141C142 –93.82°). The angle between the axial
C
phenyl planes is about 80°. Similar positions but with
slightly different torsion angles are occupied by equa-
torial and axial substituents in Ib.
Analysis of intermolecular contacts in the crystal of
I showed that the molecular packing is defined mainly
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