Oxidative addition of triorganotin halides to platinum(0) complexes

Abstract

Triorganotin chlorides react with complexes of Pt⁰ to give products of insertion into the Sn–C rather than the Sn–Cl bond as reported previously. Products of the type cis-[PtR(PPh₃)₂(SnR′₂X)](R = Ph, R′₂X = Ph₂Cl, MePhCl, Me₂Cl, BrPh₂, Ph₂I, Ph₂(OH), Ph₂(ONO₂), or Ph₃) have been obtained from [Pt(C₂H₄)(PPh₃)₂] and SnPhR′₂X, cis-[PtMe(PPh₃)₂(SnMe₂Cl)] from [Pt(C₂H₄)(PPh₃)₂] and SnMe₃Cl, and cis-[PtMe(PEt₃)₂(SnMe₃)] from [Pt(PEt₃)₄] and SnMe₄. Various reactions reported to give complexes with Cl and SnR₃ ligands have been reinvestigated and shown to give complexes with R and SnR₂Cl ligands or complexes derived from them. The reported transformation of the SnPh₃ ligand into a Ph ligand and Snph₂ has not been substantiated. Complexes and product-mixtures have been characterised by ³¹P-{¹H} spectra. An approximate thermochemical analysis suggests that M–C insertion may be favoured relative to M–Cl insertion for M = Sn, Ge, and Si, with reactivity decreasing in that order. The known complex cis-[PtPh{GePh₂(OH)}(PEt₃)₂] may be formed via insertion of [Pt(PEt₃)₂] into a Ge–Ph bond.