Density Functional Theoritical Studies on Catalytic C-H Activation Reaction: Problem of Truncated Model

作者：Zhang Lei; Xu Zengping; Yu Haoyu; Fang Decai^*

来源：Chemical Journal of Chinese Universities, 2014, 35(6): 1241-1246.

DOI：10.7503/cjcu20140246

• Density function theory
• Rh-catalyst
• C-H activation
• C-C coupling
• Truncated model

Density functional theory method was employed to simulate a Rh(PPh3)(3)Cl catalyzed C-H activation/C-C cross-coupling reaction, in which three typical processes, namely, C H activation, migratory insertion and reductive elimination, were characterized. The obtained results show that the rate-determining step is migratory insertion with the free-energy barrier of 108.3 kJ/mol. In order to test the validation of truncated models, two small catalysts Rh(PMe3)(3)Cl and Rh(PH3)(3)Cl were also used to study the same coupling reaction. Our calculations suggested that truncated models led to misunderstanding of reaction mechanism and free-energy changes, especially for migratory insertion process since the steric effect and entropic contribution play a great role on these types of reactions.

• 出版日期2014-6-10
• 单位北京师范大学