Acta Phys. -Chim. Sin. ›› 2013, Vol. 29 ›› Issue (02): 279-286.doi: 10.3866/PKU.WHXB201212061

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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

QIU Yi-Xiang, WAN Ming-Da, CHEN Xian-Yang, WANG Shu-Guang   

  1. School of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240
  • Received:2012-06-27 Revised:2012-12-04 Published:2013-01-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20973109), National Undergraduate Innovation Program, China (S110ITP5009), and Undergraduate Innovation Program of Shanghai Jiaotong University, China (IPP6123, IPP6128).

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 σH―H*πC=C* orbital level. As a result, the energy differences of πC=CH―H*H―H-πC=C* decreased, and ethylene hydrogenation was facilitated. A linear correlation was observed between the activation energies and πC=CH―H*H―H-πC=C*. The more an Au(I) complex affected the σH―H*/πC=C* orbital levels, the higher its catalytic activity.

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

MSC2000: 

  • O641