Electrostatic and Charge-Induced Methane Activation by a Concerted Double C–H Bond Insertion

A mechanistically unique, simultaneous activation of two C–H bonds of methane has been identified during the course of its reaction with the cationic copper carbide, [Cu–C]⁺. Detailed high-level quantum chemical calculations support the experimental findings obtained in the highly diluted gas phase using FT-ICR mass spectrometry. The behavior of [Cu–C]⁺/CH₄ contrasts that of [Au–C]⁺/CH₄, for which a stepwise bond-activation scenario prevails. An explanation for the distinct mechanistic differences of the two coinage metal complexes is given. It is demonstrated that the coupling of [Cu–C]⁺ with methane to form ethylene and Cu⁺ is modeled very well by the reaction of a carbon atom with methane mediated by an oriented external electric field of a positive point charge