Russian Journal of Coordination Chemistry, Vol. 29, No. 2, 2003, pp. 83–88. Translated from Koordinatsionnaya Khimiya, Vol. 29, No. 2, 2003, pp. 89–94.
Original Russian Text Copyright © 2003 by Sharutin, Egorova, Pavlushkina, Pakusina, Nasonova, Pushilin, A. Gerasimenko, E. Gerasimenko, Sergienko.
m-Oxo-Bis[(arenesulfonato)triphenylantimony]:
Synthesis and Structure
V. V. Sharutin, I. V. Egorova, I. I. Pavlushkina, A. P. Pakusina, N. V. Nasonova, M. A. Pushilin,
A. V. Gerasimenko, E. A. Gerasimenko, and A. S. Sergienko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 109, Vladivostok, 690022 Russia
Received July 12, 2001
Abstract—µ-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and µ-oxo-bis[(2,5-dimethylbenze-
nesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph3Sb with tri-p-tolylbis-
muth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in
toluene in the presence of air moisture.According yo X-ray diffraction data, the antimony atoms in the compounds
synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and
180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) Å) and Sb···S(1,2) (3.521(2),
3.559(2) Å) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) Å.
In the antimony compounds with the general for- ϕ = 0°, 90°, 180°, and 270°; (ω scan mode with a step
mula (Ar3SbX)2O, the SbOSb fragment is known to of 0.2° and 10 s per frame). The crystal–detector dis-
have a linear or a bent geometry [1–15]. To determine tance was 45 mm.
the factors influencing the SbOSb angle, the molecular
The structures were solved by direct methods and
and crystal structures of µ-oxo-bis[(4-methylbenzene-
refined by the full-matrix least-squares method in an
sulfonato)triphenylantimony] (I) and µ-oxo-bis[(2,5-
anisotropic approximation for all nonhydrogen atoms.
dimethylbenzenesulfonato)triphenylantimony
were studied in this work.
(II)
The positions of the hydrogen atoms were determined
geometrically and refined in the rider model.
The data collection, processing and refinement of the
unit cell parameters were performed using the SMART
and SAINT-Plus programs [16]. All calculations for the
determination and refinement of the structure were per-
formed using the SHELXTL/PC program [17].
EXPERIMENTAL
Synthesis of I. A mixture containing 0.50 g of tri-p-
tolylbismuth bis(4-methylbenzenesulfonate) and 0.20 g
of triphenylstibine in 30 ml of toluene was kept in a
glass evacuated tube at 25°ë for 72 h. Large crystals
formed on the tube walls were collected, dried, and
weighted; 0.15 g (88%) of µ-oxo-bis[(4-methylbenze-
nesulfonato)triphenylantimony] was thus obtained (mp
215°C). The solvent was removed from mother liquor,
and the residue was recrystallized from water. The yield
was 0.30 g (94%); (mp 220°C).
Selected crystallographic data and the results of the
structure refinement are presented in Table 1, the coor-
dinates of atoms and their equivalent isotropic thermal
parameters are given in Table 2, and selected bond
lengths and angles are listed in Table 3.
IR spectrum of I (ν, cm–1): 1300m, 1265vs;
1145vs; 1100vs; 1045w, 1020m, 970vs.
RESULTS AND DISCUSSION
Triarylstibine is known to be oxidized with hydro-
gen peroxide in the presence of arenesulfonic acids to
yield µ-oxo-bis[(arenesulfonato)triarylantimony] [15].
We established that antimony compounds of this type
can be obtained in a high yield via the reaction of tri-
phenylstibine with tri-p-tolylbismuth bis(arene-
sulfonates) in ether in the presence of air moisture:
Synthesis of II. Complex II was synthesized simi-
larly, using the above-described procedure. The yield
was 87% (mp 220°C).
IR spectrum of II (ν, cm–1): 1270vs, 1150vs,
1100vs; 1060w; 1020s, 960vs.
X-ray diffraction analysis of complexes I and II
was performed on a Bruker SMART-1000 CCD diffrac-
tometer. For I, the data were collected in sets of 606,
435, and 230 scans at ϕ = 0°, 90°, and 180°, respec-
tively (ω scan mode with a step of 0.3° and 30 s per
frame). For II, sets of 909 scans were collected at
2Ph3Sb + 2p-Tol3Bi(OSO2Ar)2 + H2O
(Ph3SbOSO2Ar)2O + 2p-Tol2BiOSO2Ar
Ar = C6H4Me-4 (I), C6H3Me2-2,5 (II).
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