Diphenylphosphino(phenylthio)methane as a monodentate or bidentate chelate ligand in rhodium, iridium and ruthenium complexes, crystal structure of [(eta(5)-C(5)Me(5)) IrCl(eta(2)-Ph(2)PCH(2)SPh-P,S)]BF4 center dot Me(2)CO

Reactions of complexes [{(eta(5)-C(5)Me(5))MCl(2)}(2)] (M = Rh, Ir) and [{(eta(6)-MeC(6)H(4)Pr(i))RuCl2}(2)] with the ligand Ph(2)PCH(2)SPh in acetone solution led to neutral complexes with the general formula [(ring)MCl(2)(eta(1)-Ph(2)PCH(2)SPh-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(eta(2)Ph(2)PCH(2)SPh-P,S)]BF4 (4-6). When the removal of the chloride ligand in complexes 1-3 was carried out in the presence of a stoichiometric amount of Ph(2)PCH(2)SPh, cationic compounds containing two P-donor monodentate ligands of the type [(eta(5)-C(5)Me(5))MCl(eta(1)-Ph(2)PCH(2)SPh-P)(2)]BF4 (7 and 8) were obtained. The structure of the iridium derivative [(eta(5)-C(5)Me(5))IrCl(eta(2)-Ph(2)PCH(2)SPh-P,S)]BF4 . Me(2)CO has been determined by single-crystal X-ray diffraction methods. The complex cation contains a C(5)Me(5) 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. (C) 1997 Elsevier Science Ltd.