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The activation reactions of methane mediated by metal carbide ions M C 3  + ( M = Ir and Pt) were comparatively studied at room temperature using the techniques of mass spectrometry in conjunction with theoretical calculations. M C 3  + ( M = Ir and Pt) ions reacted with CH 4 at room temperature forming M C 2 H 2  + /C 2 H 2 and M C 4 H 2  + /H 2 as the major products for both systems. Besides that, PtC 3  + could abstract a hydrogen atom from CH 4 to generate PtC 3 H + /CH 3 , while IrC 3  + could not. Quantum chemical calculations showed that the M C 3  + ( M = Ir and Pt) ions have a linear M-C-C-C structure. The first C-H activation took place on the Ir atom for IrC 3  + . The terminal carbon atom was the reactive site for the first C-H bond activation of PtC 3  + , which was beneficial to generate PtC 3 H + /CH 3 . The orbitals of the different metal influence the selection of the reactive sites for methane activation, which results in the different reaction channels. This study investigates the molecular-level mechanisms of the reactive sites of methane activation.

The Reactive Sites of Methane Activation: A Comparison of IrC3+ with PtC3+