Facile ligand transformation from bridging thio to terminal chloromethanethiolato. Bridge opening of [Pt(μ-S)(dppf)] 2 by dichloromethane to give Pt(SCH 2Cl) 2(dppf) [dppf  Fe(C 5H 4PPh 2) 2

Abstract

Reaction of PtCl 2(dppf) or [Pt(CH 3CN) 2(dppf)][BF 4] 2 with Na 2S gives [Pt(μ-S)(dppf)] 2. This bridging thio complex rapidly undergoes nucleophilic attack on CH 2Cl 2 to give [Pt 2(μ-S)(μ-SCH 2Cl)(dppf) 2]Cl, which cleanly converts into [Pt(SCH 2Cl) 2(dppf)] with liberation of [PtCl 2(dppf)]. These reactions effectively complete a cycle which yields a chloromethanethiolato complex from Na 2S and CH 2Cl 2 via a thio complex.