甲烷被mhm=ru,rh和pd及[ruhoh]活化的反应机理的理论分析-theoretical analysis of the reaction mechanism of methane activated by mhm = ru, rh and pd and [ ru hoh ].docxVIP

In chapter 3, Theoretical calculations for the mechanism of methane catalyzed by ligated transition metal MH+ (M = Ru, Rh and Pd) have been carried out at the DFT (B3LYP) level. The results illustrate that the activation of methane by MH+ complexes is concerted reaction via one transition states, which can competitively form metal methyl and hydrogen. Both high-spin and low-spin potential energy surfaces have been characterized in detail. The stationary points of high-spin states are higher in energy than that of the low-spin states, and the whole reaction proceeds on the ground-states potential energy surfaces with a spin-allowed manner. The activation energy barriers of reactionsare located energetically below the entrance and exit channels, thus these complexes are good mediators for the activity of methane. The exothermicities of the reactions are close for Ru, Rh and Pd: 11.1, 1.2 and 5.2 kcal/mol, respectively.Chapter 4, In this paper we have carried out a theoretical investigation at the DFT (B3LYP) level of the mechanism of methane catalyzed by ligated transition metal [Ru(H)(OH)]+, and the comparison with RuH+ system has been performed. The resultsillustrate that the activation of methane by [Ru(H)(OH)]+ complex is concerted reactionvia one transition state. A crossing between high-spin and low-spin potential energy surface takes place at both the entrance and the exit channels of the reaction, so a pathway is opened up that bypasses an energetically rather unfavorable transition structure with a spin-conserving on the high spin ground state surface. The energy barrier of TS is located energetically below the entrance and exit channels, thus the complex is a good mediator for the activity of methane. The overall reaction catalyzed by the cationic[Ru(H)(OH)]+ has a free energy ΔG° of -9.9 kcal/mol.Keywords: MH+ (M = Ru, Rh and Pd); [Ru(H)(OH)]+; concerted reaction; ligand effect; Density Functional Theory (DFT).独创性声明本人声明所呈交的论文是我个人在导师指导下进行的研究工作及 取得的研究成果。尽我所知