期刊
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
卷 115, 期 1, 页码 1-5出版社
WILEY
DOI: 10.1002/qua.24751
关键词
imine; hydrogenation; rhodium thiolate complexes; catalytic mechanism; density functional theory
类别
资金
- National Natural Science Foundations of China [21375082]
- Scientific Research Fund of Binzhou University [2010Y04]
- Binzhou Science and Technology Development Plan [2013ZC0703]
The mechanism of imine hydrogenation catalyzed by thiolate complexes of Rh(III) bearing a hydrotris(3,5-dimethylpyrazolyl)borato ligand has been investigated via the density functional theory calculations. The overall catalytic cycle for heterolytic cleavage of H-2 and hydrogenation of N-benzylidenemethylamine by the model catalyst [TpRh(bdt)MeCN)] is presented in detail. The results show that the reaction proceeds via an ionic mechanism through three steps: formation of dihydrogen complex, protonation of imine and the hydride transfer process. Protonation of imine occurs after the formation of Rh(H)-S(H) moiety. For the whole catalytic cycle, the heterolytic splitting of dihydrogen is the step with the highest free energy barrier. (c) 2014 Wiley Periodicals, Inc.
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