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, HC-Pt-H, reacts with CO to form [HC-Pt-H(CO)]. Two hydrogenation and one C-C bond coupling products are identified as isomers of [HC-Pt-H(CO)] by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. Mechanistic study reveals that both CH and CO are activated by the anionic Pt atom and that the successive depletion of the negative charge on Pt drives the CO insertion into the Pt-H and Pt-C bonds of HC-Pt-H. This study represents the first example of the simultaneous functionalization of CH and CO mediated by single atomic anions.