Metal-Ligand-Anion Cooperation in C-H Bond Formation at Platinum(II).

Thermolysis of [ H (BPI)Pt(CH 3 )][OTf] (BPI = 1,3-bis(2-(4- tert -butyl)pyridylimino)isoindole) to release methane and form (BPI)Pt(OTf) is reported. Kinetic, mechanistic, and computational studies point to an unusual anion-assisted pathway that obviates the need for a higher oxidation state intermediate to couple the metal-bound methyl group with the ligand-bound hydrogen. Leveraging this insight, a triflimide derivative of the (BPI)Pt complex was shown to activate benzene, highlighting the role of the counteranion in controlling the activity of these complexes.