Synthesis and spectroscopic characterization of tetrathiometalato complexes of bismuth(III)

Abstract

The reaction of an alcoholic solution of BiCl₃ with an aqueous solution of (NH₄)₂MS₄ (M = Mo, W) in the presence of PPh₄Cl or Bu₄NBr results in the formation of the tetracoordinate bis(tetrathiometalato) complexes of Bi(III), [S₂M(µ-S)₂Bi(µ-S)₂MS₂]⁻ in good yields (70%). Alternatively, (Ph₄P)₂MS₄ or (Bu₄N)MS₄ can react with BiCl₃ in CH₂Cl₂ to give the same products in slightly higher yields. The bidentate coordination of (MS₄)₂- to Bi(III) in these complexes has been concluded based on elemental analyses, conductivity data, and infrared and electronic spectral results. This study provides the first set of examples where a main group element is bound to thiometalates in a simple tetracoordinate fashion.