Diphenylphosphino(phenylthio)methane as a monodentate or bidentate chelate ligand in rhodium, iridium and ruthenium complexes, crystal structure of [(η5-C5Me5) IrCl(η2-Ph2PCH2SPh-P,S)]BF4 · Me2CO

Article abstract of DOI:10.1016/S0277-5387(96)00494-9

Reactions of complexes [{(η⁵-C₅Me₅)MCl₂}₂] (M = Rh, Ir) and [{(η⁶-MeC₆H₄Prⁱ)RuCl ₂}₂] with the ligand Ph₂PCH₂SPh in acetone solution led to neutral complexes with the general formula [(ring)MCl₂(η¹-Ph₂PCH₂SPh-P)] (1-3). These compounds react with thallium tetrafluoroborate in acetone solution to yield new cationic complexes in which the ligand is acting in its chelate P,S-donor fashion, [(ring)MCl(η²-Ph₂PCH₂SPh-P,S)]BF ₄ (4-6), When the removal of the chloride ligand in complexes 1-3 was carried out in the presence of a stoichiometric amount of Ph₂PCH₂SPh, cationic compounds containing two P-donor monodentate ligands of the type [(η⁵-C₅Me₅)MCl (η¹-Ph₂PCH₂SPh-P)₂]BF ₄ (7 and 8) were obtained. The structure of the iridium derivative [(η⁵-C₅Me₅)IrCl(η⁵-Ph ₂PCH₂SPh-P,S)]BF₄ · Me₂CO has been determined by single-crystal X-ray diffraction methods. The complex cation contains a C₅Me₅ group occupying three coordination positions of a distorted octahedral iridium centre, a bidentate chelate P,S-bonded ligand and a chloride atom completing the coordination sphere.