Synthesis and characterization of methylbismuth(III) complexes containing dithio ligands: crystal and molecular structure of MeBi{S2COMe}(2) and transformation of MeBi{(S2COPr)-Pr-i}2 to Bi2S3

Gupta, A., Sharma, R. K., Bohra, R., Jain, V. K., Drake, J. E., Hursthouse, M. B. and Light, M. E. (2003) Synthesis and characterization of methylbismuth(III) complexes containing dithio ligands: crystal and molecular structure of MeBi{S2COMe}(2) and transformation of MeBi{(S2COPr)-Pr-i}2 to Bi2S3. Journal of Organometallic Chemistry, 678 (1-2), 122-127. (doi:10.1016/S0022-328X(03)00435-2).

Abstract

Reactions of sodium/potassium salts of xanthates, dithiocarbamates and dialkyldithiophosphates with methylbismuth dichloride have been carried out in 1:2 stiochiometric ratio in anhydrous benzene and products of the type [MeBi(S2COR)(2)] (R = Me, Et, Pr-i), [MeBi(S2CNR2)(2)] (R = Me, Et, 1/2C(4)H(8)N) and [MeBi{S2P(OR)(2)}(2)] (R = Me, Et, Pr-i) have been isolated. All of these complexes were characterized by elemental analyses and by IR and NMR (H-1, C-13 and P-31) spectra. The X-ray structure of [MeBi(S2COMe)(2)] indicates that the immediate environment around the central bismuth atom is distorted square pyramidal. However, inclusion of a significant Bi...S intermolecular bond results in pentagonal pyramidal geometry. Thermolysis of [MeBi((S2COPr)-Pr-i)(2)] in xylene indicates that it is a good precursor for preparation of Bi2S3 at low temperature.

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Contributors

Author: M. E. Light

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