Facile ligand transformation from bridging thio to terminal chloromethanethiolato. Bridge opening of [Pt(μ-S)(dppf)]2 by dichloromethane to give Pt(SCH2Cl)2(dppf) [dppf Fe(C5H4PPh2)2]

Abstract

Reaction of PtCl2(dppf) or [Pt(CH3CN)2(dppf)][BF4]2 with Na2S gives [Pt(μ-S)(dppf)]2. This bridging thio complex rapidly undergoes nucleophilic attack on CH2Cl2 to give [Pt2(μ-S)(μ-SCH2Cl)(dppf)2]Cl, which cleanly converts into [Pt(SCH2Cl)2(dppf)] with liberation of [PtCl2(dppf)]. These reactions effectively complete a cycle which yields a chloromethanethiolato complex from Na2S and CH2Cl2 via a thio complex. © 1994.