The chemistry of the mixed P,S-donor ligands [2-(1,3-dioxolan-2-yl)phenyl] diphenylphosphane (PhPOO, 1), and [2-(1,3-dithiolan-2-yl)phenyl] diphenylphosphane (PhPSS, 2) with the RuII precursors [RuCl 2(PPh3)3] and [RuCl2(4-cymene)]2 has been investigated. The structures of the resulting complexes were analysed by X-ray crystallography and 1H, 13C and 31P NMR spectroscopy, and their activity as catalysts for hydrosilylation was examined. Reaction of 1 with [RuCl2(PPh3)3] in methanol solution produced [RuCl2(PhP(OMe)2)2] (3) [with [RuCl2(MeOH)[PhP(OMe)2}(PPh3)] (3a) as a side product}, whereas the same reaction with [RuCl2(4-cymene)] 2 produced [RuCl2(PhPOO)2] (4). The dioxolane complex 4 showed fluxional behaviour by NMR spectroscopy, whereas 3 did not. Reaction of PhPSS with[RuCl2(PPh3)3] in methanol solution produced [RuCl2(PhPSS)2] (5), and reaction with [RuCl2(4-cymene)]2 produced the cationic complex [RuCl(4-cymene)(PhPSS)]+ (6) by precipitation with NaBPh 4. In solution both 5 and 6 exist in two isomeric forms, and neither shows evidence of fluxionality at room temperature. Of the complexes tested only the acetal species 3 showed any significant hydrosilylation activity. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
