C-H键活化反应的密度泛函理论模拟对简化模型的评估

doi:10.7503/cjcu20140246

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (6): 1241.doi: 10.7503/cjcu20140246

C-H键活化反应的密度泛函理论模拟对简化模型的评估

张磊, 徐增平, 于皓宇, 方德彩()

北京师范大学化学学院, 北京 100875

收稿日期:2014-03-21 出版日期:2014-06-10 发布日期:2014-05-12
作者简介:联系人简介: 方德彩, 男, 教授, 博士生导师, 主要从事计算化学研究. E-mail:dcfang@bnu.edu.cn
基金资助:
国家自然科学基金(批准号: 21373030)资助

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

ZHANG Lei, XU Zengping, YU Haoyu, FANG Decai^*()

College of Chemistry, Beijing Normal University, Beijing 100875, China

Received:2014-03-21 Online:2014-06-10 Published:2014-05-12
Contact: FANG Decai E-mail:dcfang@bnu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21373030)

摘要/Abstract

摘要：

采用密度泛函理论方法, 模拟了Rh(PPh₃)₃Cl催化的C-H键活化/C-C键偶联反应. 将反应机理分为C-H键活化、迁移插入和还原消除3个过程进行讨论. 计算结果表明, 势能面的最高点为迁移插入的过渡态, 相对于初始原料的自由能为108.3 kJ/mol. 为了探索简化计算模型对模拟反应机理的影响, 使用2种模型催化剂Rh(PMe₃)₃Cl和Rh(PH₃)₃Cl表征相同的反应过程, 结果表明配体简化模型不合理, 主要是因为PPh₃配体的空间效应和熵效应非常明显.

关键词: 密度泛函理论, Rh催化剂, C-H键活化, C-C键偶联, 简化模型

Abstract:

Density functional theory method was employed to simulate a Rh(PPh₃)₃Cl 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)₃Cl and Rh(PH₃)₃Cl 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.

Key words: Density function theory, Rh-catalyst, C-H activation, C-C coupling, Truncated model

中图分类号:

O641

TrendMD:

张磊, 徐增平, 于皓宇, 方德彩. C-H键活化反应的密度泛函理论模拟对简化模型的评估. 高等学校化学学报, 2014, 35(6): 1241.

ZHANG Lei, XU Zengping, YU Haoyu, FANG Decai. Density Functional Theoritical Studies on Catalytic C-H Activation Reaction: Problem of Truncated Model^†. Chem. J. Chinese Universities, 2014, 35(6): 1241.

图/表 6

Fig.1 Catalytic C-H activation/C-C cross-coupling reaction between imines and olefins

Fig.2 General representation of the entire catalytic cycle

Fig.3 3D-structures of some selected stationary points along reaction pathThe PPh3 ligands and the substrate Bn group are not shown completely for simplicity.

Fig.4 Free-energy profile for the entire catalytic cycleThe free-energies in parentheses are derived from the default gas-phase translational entropies in Gaussian 09 package.

Fig.5 Changes of Rh-P bond-lengths(nm) and some energetic terms(kJ/mol) upon the dissociation

Fig.6 Comparison of free-energy profiles among three calculation models

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C-H键活化反应的密度泛函理论模拟对简化模型的评估

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

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C-H键活化反应的密度泛函理论模拟对简化模型的评估

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

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