Oxidative addition of triorganotin halides to platinum(0) complexes

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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.

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