Reactivity of a Dimethylplatinum(II) Complex with the Bis(2-pyridyl)dimethylsilane Ligand: Easy Silicon–Carbon Bond Activation
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The compound [PtMe2(bps)] (1; bps = bis(2-pyridyl)dimethylsilane) undergoes easy oxidative addition with bromine, iodine, methyl iodide, or methyl triflate to give [PtBr2Me2(bps)], [PtI2Me2(bps)], [PtIMe3(bps)], or [PtMe3(OH2)(bps)][OTf], respectively. The complex [PtIMe3(bps)] is slowly hydrolyzed in solution, with cleavage of the pyridyl–silicon bonds, to give [PtIMe3(py)2] and (Me2SiO)n. In contrast, oxidation of 1 with oxygen/CF3CH2OH, hydrogen peroxide, or dibenzoyl peroxide/H2O occurs with cleavage of a methyl–silicon bond to give [PtMe(bps)-μ-{κ3N,N,O-OSiMe(2-C5H4N)2PtMe3][CF3CH2OB(C6F5)3], [PtMe3{κ3N,N,O-(2-C5H4N)2SiMeO}], or [PtMe3{κ3N,N,O-(2-C5H4N)2SiMeOH}][PhCOO], respectively. Mechanistic studies indicate that this methyl transfer from silicon to platinum occurs after oxidation to platinum(IV) and is induced by hydroxide attack at silicon.
