Selective Activation of the C-H Bond in Methane by Single Platinum Atomic Anions

Mass spectrometric analysis of the anionic products of interaction between platinum atomic anions, Pt^- , and methane, CH₄ and CD₄ , in a collision cell shows the preferred generation of [PtCH₄ ]^- and [PtCD₄ ]^- complexes and a low tendency toward dehydrogenation. [PtCH₄ ]^- is shown to be H-Pt-CH₃ ^- by a synergy between anion photoelectron spectroscopy and quantum chemical calculations, implying the rupture of a single C-H bond. The calculated reaction pathway accounts for the observed selective activation of methane by Pt^- . This study presents the first example of methane activation by a single atomic anion.