In this article, the reaction mechanism of the cation[Au(CH2)]+ and methane was investigated at the CCSD(T)-REL//B2GP-PLYP level of theory initially.A detailed analysis of geometric structure changes during the C-H bond activation was given.As a major result, based on natural bond orbital(NBO) charge and molecular orbital {analysis,} a hydride transfer mechanistic scenario from methane to [Au(CH2)]+ was identified unambiguously.Methane activation has been identified among its reaction with [M_X]++(M=Au, Ag, Cu;X=C, CH-2).Analysis for the inherent factors during the reaction of methane as a hydrogen donor is given.The M_X bond energy and the low-lying vacant orbital directly involved in the reaction of the active center C play an important role on the reaction activity, and both mediated microscopic mechanism.This study may provide important guidance for the rational design of catalysts.%在 CCSD(T)-REL//B2GP-PLYP水平下构建[Au(CH2)]+与甲烷反应的可靠反应势能面, 分析了{C-H}键活化过程中的几何结构变化情况;对反应IRC路径上关键点进行自然键轨道(NBO)电荷和分子轨道分析, 从理论上推定该氢转移过程属于氢负离子(H-)转移.对[M_X]+(M=Au, Ag, Cu;X=C, CH-2)与甲烷反应进行对比, 分析了甲烷作为氢供体反应过程的内在影响因素.M_X键能和反应活性中心C上直接参与反应的低能轨道对反应活性均起重要作用, 两者协同调控微观反应机制.
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