Reactivity of a Dimethylplatinum(II) Complex with the Bis(2-pyridyl)dimethylsilane Ligand: Easy Silicon–Carbon Bond Activation

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.