Oxidatively induced reactions of a diimine platinum(IV) tetramethyl complex

The oxidation of the Pt(IV) tetramethyl complex [Arsingle bondNdouble bond; length as m-dashCHsingle bondCHdouble bond; length as m-dashNsingle bondAr]PtMe4 (Ar = 2,6-Me2C6H3) has been investigated in acetonitrile and dichloromethane. Cyclic voltammetry demonstrates that the irreversible oxidation of [Arsingle bondNdouble bond; length as m-dashCHsingle bondCHdouble bond; length as m-dashNsingle bondAr]PtMe4 occurs at a slightly less positive oxidation potential than the irreversible oxidation of the analogous Pt(II) species [Arsingle bondNdouble bond; length as m-dashCHsingle bondCHdouble bond; length as m-dashNsingle bondAr]PtMe2. The product distribution arising from the oxidation depends strongly on the reaction conditions and includes cationic Pt(IV) species (acetonitrile, dichloromethane solvents) and Pt(II) species (dichloromethane only). Evidence is presented that suggests that homolytic cleavage of a weakened Ptsingle bondC bond in View the MathML source