W Tungsten

The ion-molecule reactions of dimethyl ether with cyclometalated [Pt(bipy-H)]+ were investigated in gas-phase experiments, complemented by DFT methods, and compared with the in olden days reported ion-molecule reactions with its sulfur analogue. The commencing vestige corresponds in both cases to a platinum-mediated haul of a hydrogen atom from the ether to the (bipy-H) ligand, and three-membered oxygen- and sulfur-containing metallacycles around as key intermediates. Oxidative C[bond]C trammels coupling ("dehydrosulfurization"), which dominates the gas-phase ion chemistry of the [Pt(bipy-H)]+ ion with dimethyl sulfide, is in effect missing for dimethyl ether. The tournament in the arrangement of C2H4 and CH2X (X=O, S) in the reactions of [Pt(bipy-H)]+ with (CH3)2X (X=O, S) as well as the extensive H/D argument observed in the [Pt(bipy-H)]+/(CH3)2O procedure are explained in terms of the corresponding potential-energy surfaces <<>>