Simultaneous Functionalization of Methane and Carbon Dioxide Mediated by Single Platinum Atomic Anions.

Mass spectrometric analysis of the anionic products of interaction among Pt-, methane, and carbon dioxide shows that the methane activation complex, H3C-Pt-H-, reacts with CO2 to form [H3C-Pt-H(CO2)]-. Two hydrogenation and one C-C bond coupling products are identified as isomers of [H3C-Pt-H(CO2)]- by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. Mechanistic study reveals that both CH4 and CO2 are activated by the anionic Pt atom and that the successive depletion of the negative charge on Pt drives the CO2 insertion into the Pt-H and Pt-C bonds of H3C-Pt-H-. This study represents the first example of the simultaneous functionalization of CH4 and CO2 mediated by single atomic anions.