The preparation and structural characterisation of thiolato anions of bismuth(III)

The preparation and structures of the bismuth thiolato anions [Bi2(SC6F5)6(μ-SC6F5)]− and [Bi2(SC6F5)6(μ-SC6F5)2]2− and the halothiolato anions [Bi2(SC6F5)6(μ-Br)]−, [Bi2(SC6F5)6(μ-Cl)2]2− and [Bi3(SC6F5)9(μ-Br)2]2− are described. All compounds have been isolated from reactions between Bi(SC6F5)3 and ammonium or phosphonium halides. The basic structural units in the dinuclear species are of two types namely [Bi2(SR)6(μ-X)]− and [Bi2(SR)6(μ-X)2]2−, where X=thiolate or halide. In the former case the single bridging groups occupy an axial site within the disphenoidal (equatorially vacant, trigonal bipyramidal) geometry around the bismuth centres whereas in the latter the two bridging groups occupy cis basal sites in square based pyramidal bismuth environments. The trinuclear anion [Bi3(SC6F5)9(μ-Br)2]2− has features in common with the basic [Bi2(SC6F5)6(μ-Br)]− unit.