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.