Dinuclear rhodium-rhodium and rhodium-palladium complexes with different bridging ligands. Crystal structure of [Rh2(μ-SPPh2)(μ-Cl)(COD)2]

Article abstract of DOI:10.1016/0022-328X(95)06003-F

Homo- and hetero-dinuclear complexes of general formulae [Rh₂(μ-SPPh₂)(μ-Cl)(diolefin)₂] (diolefin = 1,5-cyclooctadiene (COD) (1), tetrafluorobenzobarrelene (TFB) (2)) and [RhPd(μ-SPPh₂)(μ-Cl)(diolefin)(η³-C₃H₅)] (diolefin = COD (4), 2,5-norbornadiene (NBD) (5)), containing one chloride anion and one thiophosphinito group as bridging ligands, have been synthesised by redistribution reactions starting from the corresponding homo-bridged compounds [Rh₂(μ-SPPh₂)₂(diolefin)₂], [Rh₂(μ-Cl)₂(diolefin)₂] or [Pd₂(μ-Cl)₂(η³-C₃H₅)₂]. The structural X-ray analysis carried out for one member of this series, [Rh₂(μ-SPPh₂)(μ-Cl)(COD)₂], has shown the bridging P,S-coordination of the thiophosphinito ligand. The intermetallic separation, 3.291(2) A, excludes any significant direct metal-metal interaction.