On the Activation of Chloromethanes by Cyclometalated [Pt(bipy - H)]+ in the Gas Phase: A Mechanistic Study

In the ion/molecule reactions of cyclometalated [Pt(bipy - H)]+ with the chloromethanes CH4-nCln+ (n = 1-4) insertion of platinum into the C-Cl bond corresponds to the first step. Next, a 1,2-methyl shift results in C-C bond coupling for substrates with n = 1-3; afterwards, HCl is lost with the hydrogen atom originating from either the incoming substrate or from the (bipy - H) ligand. In the reaction with CH2Cl2, the most dominant process corresponds to a CH2 transfer to the (bipy - H) ligand concomitant with the formation of neutral PtCl2.