Autoxidation of platinum(IV) hydrocarbyl hydride complexes to form platinum(IV) hydrocarbyl hydroperoxide complexes.

The platinum(IV) hydride complexes Tp(Me(2))PtR(2)H (Tp(Me(2)) = hydridotris(3,5-dimethylpyrazolyl)borate, R = Me (1a), Ph (1b)) react with molecular oxygen to form platinum(IV) hydroperoxide complexes Tp(Me(2))PtR(2)OOH (R = Me (2a) and Ph (2b), respectively) in high yield. The results of kinetic and mechanistic studies of these reactions are consistent with the net insertion of molecular oxygen into the Pt(IV)-H bonds occurring via radical chain mechanisms. The radical chain pathways resemble, in many respects, those documented for autoxidations of organic substrates, but significant differences are also evident.