Methylplatinum(II) and Molecular Oxygen: Oxidation to Methylplatinum(IV) in Competition with Methyl Group Transfer To Form Dimethylplatinum(IV)

Reaction of molecular oxygen with the methylplatinum­(II) complex K­[(κ2-NNO)­PtII(CH3)­(OH)] (3; NNO = bis­(3,5-dimethylpyrazol-1-yl)­acetate) in D2O results in oxidation to (κ3-NNO)­PtIV(CH3)­(OD)2 along with competitive methyl transfer to produce (κ3-NNO)­PtIV(CH3)2(OD). Methyl transfer is favored under more alkaline conditions and at higher temperatures. Mechanistic studies are consistent with the direct reaction of 3 with molecular oxygen as a common first reaction step on the path to both products.