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Issue 16, 2003
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Coordination complexes of the bismuth(iii) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridineligands

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The chloro-aryl bismuth thiolate Bi(SC6Cl5)3 has been prepared from the reaction between BiPh3 and the thiol HSC6Cl5 by analogy with the previously described synthesis of the fluoro-aryl species Bi(SC6F5)3. The compound Bi(SC6Cl5)3 is only sparingly soluble but can be isolated as a dmf adduct [Bi(SC6Cl5)3(dmf)2] (dmf = N,N-dimethylformamide) which adopts a five-coordinate square-based pyramidal geometry in which the two dmf ligands lie in the basal plane with a mutually cis configuration. Treatment of either Bi(SC6F5)3 or Bi(SC6Cl5)3 with pyridine or 2,2′-bipyridyl ligands affords the coordination complexes fac-[Bi(SC6F5)3(py)3] (two crystalline polymorphs), fac-[Bi(SC6Cl5)3(py)3], fac-[Bi(SC6F5)3(4-pic)3] (4-pic = 4-picoline), [Bi(SC6Cl5)3(4-pic)2], [Bi(SC6F5)3(bipy)] (bipy = 2,2′-bipyridyl), [Bi(SC6Cl5)3(bipy)], [Bi2(SC6Cl5)6(2-pic)3] (2-pic = 2-picoline) and [Bi(SC6F5)3(4-pic)]. Five- and four-coordinate complexes adopt square-based pyramidal and equatorially vacant, trigonal bipyramidal (disphenoidal) geometries respectively, the former having the two ligands cis to each other in the basal plane. The compound [Bi2(SC6Cl5)6(2-pic)3] contains both five- and four-coordinate mononuclear units. A salt with the formula [4-picH][(4-pic)2H][Bi3(SC6F5)11] was also isolated in which the anion contains a central bismuth bonded to five thiolate ligands with a square-based pyramidal geometry. Two cis-basal thiolates act as bridging groups to two outer bismuth centres each of which is four-coordinate with the expected disphenoidal geometry in which the bridging thiolate is in an axial position. The structure of the dinuclear arylbismuth thiolate compound [Bi2Ph2(SC6F5)4(4-pic)2] is also described. Intramolecular conformations and intermolecular associations in all structures are dominated by π–π-interactions.

Graphical abstract: Coordination complexes of the bismuth(iii) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands

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Supplementary files

Article information

21 May 2003
25 Jun 2003
First published
14 Jul 2003

Dalton Trans., 2003, 3270-3277
Article type

Coordination complexes of the bismuth(III) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands

K. M. Anderson, C. J. Baylies, A. H. M. Monowar Jahan, N. C. Norman, A. G. Orpen and J. Starbuck, Dalton Trans., 2003, 3270
DOI: 10.1039/B305711A

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