物理化学学报 >> 2014, Vol. 30 >> Issue (5): 821-828.doi: 10.3866/PKU.WHXB201403241

理论与计算化学 上一篇    下一篇

镍催化芳烃卤化物还原性交叉偶联的反应机理

蒋峰, 任清华   

  1. 上海大学理学院化学系, 上海200444
  • 收稿日期:2013-12-10 修回日期:2014-03-21 发布日期:2014-04-25
  • 通讯作者: 任清华 E-mail:qinghua.ren@shu.edu.cn
  • 基金资助:

    上海大学高性能计算平台“自强4000”与上海市高等教育内涵建设“085”工程“材料基因工程”项目(B.58-B111-12-101,B.58-B111-12-103)资助

Reaction Mechanism for the Ni-Catalyzed Reductive Cross-Coupling of Aryl Halides

JIANG Feng, REN Qing-Hua   

  1. Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. China
  • Received:2013-12-10 Revised:2014-03-21 Published:2014-04-25
  • Contact: REN Qing-Hua E-mail:qinghua.ren@shu.edu.cn
  • Supported by:

    The project was supported by the High Performance Computing Platform of Shanghai University, China and Shanghai Higher Education Connotation Construction "085" Project "Materials Genome Engineering" Funding, China (B.58-B111-12-101, B.58-B111-12-103).

摘要:

利用密度泛函理论(DFT)计算研究了镍催化的溴苯(R1)与对溴苯甲酸甲酯(R2)生成非对称联芳化合物的还原性交叉偶联反应的机理. 结果表明,相对于一价镍的催化机理,零价镍作为活性催化剂更有利于反应的进行,零价镍催化剂首先与R1络合或者首先与R2络合的反应机理十分相似,其决速步在气相时的能垒分别是70.50或者49.66 kJ·mol-1. 零价镍催化机理包括如下步骤:一次氧化加成;还原;二次氧化加成;还原消除以及催化剂再生. 另外,计算结果还表明有机锌试剂在这个反应体系中很难生成.

关键词: 密度泛函理论, 镍催化, 还原性交叉偶联, 反应机理, 不对称联苯

Abstract:

The mechanism of the Ni-catalyzed reductive cross-coupling reaction of bromobenzene (R1) and methyl 4-bromobenzoate (R2) to form an unsymmetrical biaryl system has been theoretically investigated using density functional theory calculations. Our results showed that the Ni0-catalyzed process was favored over the NiI-catalyzed mechanism. The mechanism for the reaction of the Ni0 catalyst initially attacking either R1 or R2 was quite similar, where the energy barrier in the gas phase for the rate-limiting step was 70.50 or 49.66 kJ·mol-1, respectively. The mechanism in the favored Ni0-catalyzed reaction involved the following steps: first oxidative addition, reduction, second oxidative addition, reductive elimination, and catalyst regeneration. Our calculated results also indicated that no organometallic reagents were produced in the reaction cycle.

Key words: Density functional theory, Nickel catalysis, Reductive cross-coupling, Reaction mechanism, Unsymmetrical biaryl

MSC2000: 

  • O641