摘要
The mechanism of the reaction of Ni^+ (~2D) with ethane in the gas-phase wasstudied by using density functional theory. Both the B3LYP and BLYP functionals with standardall-electron basis sets are used to give the detailed information of the potential energy surface(PES) of [Ni, C_2, H_6]^+. The mechanisms forming the products CH_4 and H_2 in the reaction of Ni^+with ethane are proposed. The reductive eliminations of CH_4 and H_2 are typicaladdition-elimination reactions. Each of the two reactions consists of two elementary steps; C―C orC―H bond activations to form inserted species followed by isomerizations to form product-likeintermediate. The rate determining steps for the elimination reactions of forming CH_4 and H_2 arethe isomerizations of the inserted species rather than C―C or C―H bond activations. Theelimination reaction of forming H_2 was found to be thermodynamically favored compared to that ofCH_4.
The mechanism of the reaction of Ni^+ (~2D) with ethane in the gas-phase wasstudied by using density functional theory. Both the B3LYP and BLYP functionals with standardall-electron basis sets are used to give the detailed information of the potential energy surface(PES) of [Ni, C_2, H_6]^+. The mechanisms forming the products CH_4 and H_2 in the reaction of Ni^+with ethane are proposed. The reductive eliminations of CH_4 and H_2 are typicaladdition-elimination reactions. Each of the two reactions consists of two elementary steps; C―C orC―H bond activations to form inserted species followed by isomerizations to form product-likeintermediate. The rate determining steps for the elimination reactions of forming CH_4 and H_2 arethe isomerizations of the inserted species rather than C―C or C―H bond activations. Theelimination reaction of forming H_2 was found to be thermodynamically favored compared to that ofCH_4.
基金
ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No.2 0 1330 2 0 )
