Bismuth(III) complexes derivatives of phosphinothiol ligands: The crystal structure of [Bi{2-(Ph2P)C6H4S}3]

Neutral Bi(III) complexes of a series of phosphinothiol ligands, 2-(Ph2P)C6H4SH, 2-(Ph2P)6-(Me3Si)C6H3SH, PhP(C6H4SH-2)2 and P(C6H4SH-2)3 have been prepared by direct reaction of bismuth(III) chloride and the appropriate ligand in methanol in the presence of triethylamine. All compounds were characterized by microanalysis, FAB mass spectrometry, IR, 1H and 31P NMR spectroscopy. The crystal structure of the complex [Bi{2-(Ph2P)C6H4S}3] was determinated by X-ray diffraction. The bismuth ion is hexacoordinated by three anionic phosphinothiolate ligands, which act in a bidentated chelating (S,P) manner. The coordination geometry around the metal ion can be described as distorted octahedral.

A series of phosphinothiolate complexes of Bi(III) have been prepared in methanol by reacting bismuth(III) chloride with 2-(Ph2P)C6H4SH, 2-(Ph2P)6-(Me3Si)C6H3SH, PhP(C6H4SH-2)2 and P(C6H4SH-2)3 ligands in presence of Et3N. The crystal structure of complex [Bi{2-(Ph2P)C6H4S}3] was also determinated and represents the first Bi(III) compound coordinated by P and S, structurally characterized by X-ray crystallography. The bismuth ion is coordinated by three thiolate ligands, all of them acting as bidentated through the sulfur and phosphorous atoms. The coordination geometry around the metal ion can be described as distorted octahedral. Spectral data of the complexes (IR, NMR and FAB-MS) are also discussed and related to the structural information.Figure optionsDownload as PowerPoint slide