Pt+-mediated activation of methane: theory and experiment

A combined theoretical and experimental study on the Pt+-mediated activation of methane is presented. Dehydrogenation of CH4 by thermalized Pt+ cations (Pt+ + CH4 ← PtCH2+ + H2) proceeds along a doublet ground state potential energy surface and is found to be reversible under the conditions of Fourier transform ion-cyclotron resonance mass spectrometry. The recently reported oxidation of the cationic platinum carbene PtCH2+ by O2 produces electronically excited Pt+ cations, which are detected in the 4F92 state by means of charge-transfer bracketing experiments.