A computational study on the intriguing mechanisms of the gas-phase thermal activation of methane by bare [Ni(H)(OH)]+

A detailed computational study on the reaction mechanisms of the thermal activation of methane by the bare complex [Ni(H)(OH)]⁺ has been conducted. The experimentally observed reaction features, i.e. the ligand exchange Ni(H) → Ni(CH₃), the H/D scrambling between the incoming methane and the hydrido ligand of the nickel complex, the spectator-like behavior of the OH ligand, and the relatively moderate reaction efficiency of 6% relative to the collision rate of the ion/molecule reaction, can be explained by considering three competing mechanisms, and a satisfactory agreement between experiment and theory has been found.