Citation: QIU Yi-Xiang, WAN Ming-Da, CHEN Xian-Yang, WANG Shu-Guang. Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by ld(I) Complexes[J]. Acta Physico-Chimica Sinica, ;2013, 29(02): 279-286. doi: 10.3866/PKU.WHXB201212061 shu

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

1.
School of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240

Received Date: 27 June 2012
Available Online: 6 December 2012
Fund Project: 国家自然科学基金(20973109) (20973109) 国家大学生创新性实验计划(S110ITP5009) (S110ITP5009)上海交通大学大学生创新实践计划(IPP6123, IPP6128)资助项目 (IPP6123, IPP6128)

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.
- Density functional theory,
- Ethylene hydrogenation,
- ld(I) complex,
- Reaction mechanism,
- Electronic structure
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