Russian Journal of Coordination Chemistry, Vol. 29, No. 7, 2003, pp. 468–473. Translated from Koordinatsionnaya Khimiya, Vol. 29, No. 7, 2003, pp. 502–507.
Original Russian Text Copyright © 2003 by Sharutin, Egorova, Ivanenko, Sharutina, Popov.
Synthesis and Crystal Structure of Tetraphenylbismuth
Benzenesulfonate Hydrate and Tetraphenylbismuth
3,4-Dimethylbenzenesulfonate
V. V. Sharutin, I. V. Egorova, T. K. Ivanenko, O. K. Sharutina, and D. Yu. Popov
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received March 19, 2002
Abstract—The reaction of pentaphenylbismuth with SO3 or with triphenylbismuth bis(benzenesulfonate) in
benzene gave tetraphenylbismuth benzenesulfonate monohydrate (I). Tetraphenylbismuth 3,4-dimethylbenze-
nesulfonate (II) was prepared from pentaphenylbismuth and triphenylbismuth bis(3,4-dimethylbenzene-
sulfonate) in benzene. The structures of compounds I and II were established by X-ray diffraction. The Bi
atoms have a distorted trigonal-bipyramidal coordination where the arenesulfonate group occupies an axial
position. The Bi–C(average) and Bi–O distances in molecules I and II are 2.204(2), 2.695(2) Å and 2.205(2),
2.728(2) Å, respectively.
Tetraphenylbismuth arenesulfonates (Ph4BiOSO2Ar) 50 ml of benzene was stirred for 1 h at 20°ë in a glass
are usually prepared either from pentaphenylbismuth evacuated tube. The solvent was then removed, and the
(Ph5Bi) and arenesulfonic acid by a substitution reac- residue was recrystallized from a benzene–heptane
tion [1] or from pentaphenylbismuth and triphenylbis- mixture (5 : 1) to give 1.98 g (84%) of compound II
muth bis(arenesulfonates) (Ph3Bi(OSO2Ar)2) by a rad- (mp 168°C).
ical redistribution reaction [2, 3]. Here we propose a
Synthesis of triphenylbismuth bis(3,4-dimethyl-
new method for the synthesis of tetraphenylbismuth
benzenesulfonate)
(III).
3,4-Dimethylbenzene-
benzenesulfonate hydrate (I) from pentaphenylbismuth
and sulfur oxide SO3 at room temperature in a benzene
solution.
sulfonic acid (0.85 g) and a 30% solution of hydrogen
peroxide (0.29 ml) were added to a solution of triphen-
ylbismuth (1 g) in 20 ml of ether (the reactant molar
ratio was 1 : 2 : 1). After 12 h, the obtained colorless
crystals were collected and dried. The yield of com-
pound III was 1.84 g (72%) (decomposes at 133°C).
EXPERIMENTAL
Synthesis of I. (a) A stream of SO3, prepared by
burning sulfur (0.35 g) in oxygen in the presence of a
catalyst (V2O5), was passed through a solution of Ph5Bi
(1 g) in 20 ml of benzene for 7 min at 25°ë. After
removal of the solvent, the residue was recrystallized
from water. The yield of compound I was 0.58 g (50%)
(mp 129°ë). IR (ν, cm–1): 1640 w, 1565 w, 1245 vs,
IR spectra were recorded on a Hitachi-215 spec-
trometer (mineral oil mull between NaCl plates).
X-Ray diffraction analysis of crystals I and II was
carried out on a SMART 1000 CCD automated diffrac-
tometer (MoKα radiation, λ 0.71073 Å).
The crystals of I are monoclinic; at 20°ë, a =
1165 m, 1145 vs, 1115 s, 1030 w, 1010 s, 982 vs. (b) A 13.805(1) Å, b = 11.939(1) Å, c = 17.820(2) Å; β =
mixture of Ph5Bi (0.54 g), triphenylbismuth bis(benze- 107.616(2)°, V = 2728.0(5) Å3, space group P21/c, Z =
nesulfonate) (0.68 g), and 20 ml of toluene was stirred 4, ρ(calcd) = 1.686 g/cm3, crystal dimensions 0.25 ×
for 20 min at 20°ë in a glass evacuated tube. The sol- 0.25 × 0.25 mm, µMo = 6.570 mm–1, 2θ < 30°. The final
vent was removed and the residue was recrystallized R-factors were R1 = 0.0554, wR2 = 0.0552 for all 19466
from water. The yield of compound I was 0.70 g (56%). reflections; and R1 = 0.0274, wR2 = 0.0517 for the 4832
(c) A mixture of benzenesulfonic acid (0.26 g) and reflections with I > 2σ(I). The data were collected in
Ph5Bi (1 g) in 20 ml of acetone was kept for 10 min at groups of 606, 430, and 240 shots for angles ϕ of 0°,
20°ë. The solvent was removed and the residue was 90°, and 180°, respectively; ω scanning was done with
recrystallized from water to give 0.62 g (53%) of com- a step of 0.3° and an exposure of 10 s per shot.
pound I.
The crystals of II are orthorhombic; at 23°ë, a =
Synthesis of tetraphenylbismuth 3,4-dimethylben- 9.936(1) Å, b = 16.169(2) Å, c = 17.484(2) Å; V =
zenesulfonate (II). A mixture of Ph5Bi (1 g), triphenyl- 2808.7(5) Å3, space group P212121, Z = 4, ρ(calcd) =
bismuth bis(3,4-dimethylbenzenesulfonate) (1.36 g), and 1.662 g/cm3, crystal dimensions 0.22 × 0.25 × 0.32 mm,
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