Chem. J. Chinese Universities ›› 2018, Vol. 39 ›› Issue (4): 721.doi: 10.7503/cjcu20170652

• Physical Chemistry • Previous Articles     Next Articles

Theoretical Study on the Formation Mechanism of Catalytic Active Components in Suzuki-Miyaura Cross-Coupling Reaction Catalyzed by Transition Metal Cobalt Complex

ZHANG Wei1, ZHANG Yiwei1, LI Hui1,2, LEI Ming1,*()   

  1. 1. State Key Laboratory of Chemical Resource Engineering, College of Science,Beijing University of Chemical Technology, Beijing 100029, China
    2. Chemical Science and Engineering College, North Minzu University, Yinchuan 750021, China
  • Received:2017-09-29 Online:2018-04-10 Published:2018-03-21
  • Contact: LEI Ming E-mail:leim@mail.buct.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21672018, 21373023), the Natural Science Foundation of Beijing City, China(No.2162029) and the Fundamental Research Funds for the Central Universities, China(No.PYCC1708)

Abstract:

The reaction mechanism of Co(Ⅰ) complex (iPrPNP)CoOR formation in Suzuki-Miyaura cross-coupling reaction catalyzed by cobalt complex was studied via density functional theory(DFT) calculation. The calculated results indicate that a phosphine ligand in the diisopropyl-substituted bis(phosphino)pyridine pincer ligand(iPrPNP) is dissociated from the Co metal center to produce INT1', the dissociative path at triplet state is the most favorable reaction path to form (iPrPNP)CoOR than the non-dissociative path. The concerted mechanism of Co(Ⅰ) complex (iPrPNP)CoOR produced by INT1' is more favorable than the stepwise mechanism in the dissociative path. The effect of substituent groups of substrate HOR was studied, which in agreement with experimental observations. The reaction mechanism could provide a theoretical insight into the whole Suzuki-Miyaura cross-coupling reaction mechanism.

Key words: Transition metal cobalt complex, Dissociative path, Density functional theory, Concerted mechanism

CLC Number: 

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