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

Homo- and hetero-dinuclear complexes of general formulae [Rh2(-SPPh2)(-Cl)(dìolefin)2] (diolefin = 1,5-cyclooctadiene (COD) (1), tetrafluorobenzobarrelene (TFB) (2)) and [RhPd(-SPPh2)(-Cl)(diolefin)(3-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(-SPPh2)2(diolefin)2], [Rh2(-Cl)2(diolefin)2] or [Pd2(-Cl)2(3-C3H5)2]. The structural X-ray analysis carried out for one member of this series, [Rh2(-SPPh2)(-Cl)(COD)2], has shown the bridging P,S-coordination of the thiophosphinito ligand. The intermetallic separation, 3.291(2) Å, excludes any significant direct metal-metal interaction