金(I)配合物催化乙烯加氢的反应机理

doi:10.3866/PKU.WHXB201212061

Abstract

Abstract:

The reaction mechanisms of ethylene hydrogenation catalyzed by Au(I) complexes AuX (X=F, Cl, Br, I) and AuPR₃⁺ (R = F, Cl, Br, I, H, Me, Ph) were investigated using density functional theory at the B3LYP level. The calculated results indicated that Au(I) complexes were effective catalysts in the hydrogenation of ethylene. AuPR₃⁺ showed higher catalytic activity than AuX and the effect of changing the electron donating or withdrawing ability of the ligand on catalytic activity was large. Natural bond orbital analysis indicated that the interactions between the Au(I) complex and H₂/C₂H₄ not only weakened the H― H/C＝C bond strength, but also decreased the energy of the σ_H―H^*、π_C＝C^* orbital level. As a result, the energy differences of π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^* decreased, and ethylene hydrogenation was facilitated. A linear correlation was observed between the activation energies and π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^*. The more an Au(I) complex affected the σ_H―H^*/π_C＝C^* orbital levels, the higher its catalytic activity.

Key words: Density functional theory, Ethylene hydrogenation, Gold(I) complex, Reaction mechanism, Electronic structure

QIU Yi-Xiang, WAN Ming-Da, CHEN Xian-Yang, WANG Shu-Guang. Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by Gold(I) Complexes[J]. Acta Phys. -Chim. Sin. 2013, 29(02), 279-286. doi: 10.3866/PKU.WHXB201212061

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Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by Gold(I) Complexes

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