Russian Journal of Coordination Chemistry, Vol. 30, No. 12, 2004, pp. 874–883. Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 925–934.
Original Russian Text Copyright © 2004 by Sharutin, Egorova, Sharutina, Dorofeeva, Ivanenko, Gerasimenko, Pushilin.
Synthesis and Structure of Bismuth-Containing Complexes
[(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}]+2 [Ph2Bi2I6]2–,
[(Ph4Bi]+[PhBi(C5H5N)I3]–, [Ph4Sb]+4 [Bi4I16]4– · 2(CH3)2C=O,
and [Ph4Sb]+3 [Bi5I18]3–
V. V. Sharutin*, I. V. Egorova*, O. K. Sharutina*, O. A. Dorofeeva*, T. K. Ivanenko*,
A. V. Gerasimenko**, and M. A. Pushilin**
* Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
** Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received January 8, 2003
Abstract—The reactions of tetraphenylbismuthonium and -stibonium salts Ph4EX (E = Bi, Sb; X = I,
OSO2(C6H3(CH3)2-2,5), OSO2C6H3(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes
[Ph4Bi]+[PhBi(C5H5N)I3]–,
[(Ph4BiO)2S(O){2,5-(CH3)2C6H3S(O)}m]+2 [Ph2Bi2I6]2–,
[Ph4Sbm]+4 [Bi4I16]4–
·
2(CH3)2C=O, and [Ph4Sbm]+3 [Bi5I18]3–, whose structural units, according to the X-ray diffraction data, are tet-
raphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.
INTRODUCTION
dried. Complex II was obtained in 67% yield (0.27 g),
Tdecomp > 200°C.
The reactions of tetraphenylantimony halides with
phenylbismuth bis(arenesulfonates) are known to
afford complexes containing tetraphenylstibonium cat-
ions and cyclic bismuth-containing anions [1, 2]. To
continue our studies in this direction, we studied the
reactions of tetraphenylbismuthonium (-stibonium)
salts with bismuth triiodide and determined crystal
structures of four products of these reactions.
Synthesis of [Ph4Sb]+4 [Bi4I16]4– · 2(CH3)2C=O
(III). A solution of tetraphenylantimony iodide (0.50 g)
in acetone (20 ml) was added to a solution of bismuth
triiodide (0.53 g) in acetone (50 ml), and the reaction
mixture was stored for 12 h. After the solvent was evap-
orated, red-cherry crystals of compound III were
obtained in 90% yield (0.95 g), Tm = 128°ë.
Synthesis of [Ph4Sb]+3 [Bi5I18]3– (IV). A solution of
EXPERIMENTAL
tetraphenylantimony
2,5-dimethylbenzenesulfonate
Synthesis
of
[(Ph4BiO)2{2,5-
(0.50 g) in acetone (20 ml) was added to a solution of bis-
muth triiodide (0.80 g) in acetone (80 ml), and the reaction
mixture was stored for 12 h. Large red-cherry crystals of
compound IV were obtained in 44% yield (0.55 g) on
slow evaporation of the solvent, Tm = 156°ë (decomp.).
(CH3)2C6H3S(O)}]2+ [Ph2Bi2I6]2– (I). A solution of bis-
muth triiodide (0.39 g) in acetone (20 ml) was added to
a solution of tetraphenylbismuth 2,5-dimethylbenzene-
sulfonate (0.50 g) in acetone (20 ml), and the reaction
mixture was stored for 12 h. Red-orange crystals that
formed were filtered and dried. The yield of complex I
was 67% (0.60 g), Tm = 116°ë (140°ë decomp.).
Synthesis of [Ph4Bi]+[PhBi(C5H5N)I3]– (II). Pyri-
dine (10 ml) was added to a mixture of tetraphenylbis-
muth 3-carboxy-4-oxybenzenesulfonate (0.30 g) and
bismuth triiodide (0.19 g) in acetone (10 ml), and the
reaction mixture was stirred for 12 h. The reaction mix-
ture was concentrated to a volume of 5 ml and cooled
X-ray diffraction analyses of crystals of compounds
I–IV were carried out on a SMART 1000 CCD diffrac-
tometer (graphite monochromator, MoKα radiation, λ =
0.71073 Å). The structures were determined by the direct
method and refined by the least-squares method in the
anisotropic approximation for non-hydrogen atoms. The
positions of H atoms were calculated geometrically and
included into the “riding” model refinement.
The data were collected and processed and the unit
to –18°ë. Yellow crystals that formed were filtered and cell parameters were refined using the SMART and
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