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

Abstract

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