Mechanistic studies of reactions of benzenethiol with methyl derivatives of platinum(II) and gold-(I) and -(III)
Abstract
Benzenethiol reacts with the complexes [MeAuL], [Me3AuL], and cis-[PtMe2L2](L = PMe3, PMe2Ph, PMePh2, or PPh3) to give methane and [(PhS)AuL], cis-[Me2Au(SPh)L], and trans-[PtMe(SPh)L2] or trans-[Pt(SPh)2L2] respectively. The reactions with the gold(I) and platinum(II) complexes proceed by free-radical chain mechanisms, but the gold(III) complexes react by a non-radical mechanism. Competitive reactions with benzenethiol show the order of reactivity [MeAu(PMe3)] > [MeAu(PMePh2)] > [MeAu(PPh3)], cis-[PtMe2(PMe2Ph)2] > trans-[PtMe(SPh)(PMe2Ph)2][Me3Au(PMe3)], [Me3Au(PMePh2)]
cis-[Me2Au (SPh)(PMe3)].