The metal is the kinetic site of protonation of (Diimine)Pt dimethyl complexes

Article abstract of DOI:10.1021/ja027649j

Protonolysis of (diimine)PtMe₂ (1) complexes in CD₂Cl₂ containing CD₃CN at -78 °C yields (diimine)PtMe₂(H)(NCCD₃)⁺ (4), (diimine)PtMe(NCCD₃)⁺ (5), and methane. The relative yields of 5 and methane decrease with increasing concentrations of CD₃CN. This is consistent with protonation of 1 occurring directly at the metal, rather than at a methyl group. The principle of microscopic reversibility then implies that the deprotonation in Shilov-type C-H activation occurs from a Pt(IV) hydridomethyl intermediate, rather than from a Pt σ-methane complex. Copyright