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Keywords:

  • C–H activation;
  • methane;
  • photoionization;
  • platinum;
  • reaction intermediates
Thumbnail image of graphical abstract

Does Charge Matter? Direct vacuum UV measurement of ionization energies reveals that C–H insertion by Pt to form H-Pt-CH3 is highly exoergic, while production of PtCH2+H2 is slightly endoergic. Experiments and spin-orbit DFT calculations reveal surprisingly similar energetics for dehydrogenation of methane by neutral and cationic platinum. Red lines in the picture indicate experimentally determined energies.