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A computational investigation of the hydrogenation of imines catalyzed by rhodium thiolate complexes

Authors

  • Honghong Zhang,

    1. Department of Chemical Engineering and Materials Science, College of Chemistry, Shandong Normal University, Jinan, People's Republic of China
    2. Department of Chemical Engineering, Binzhou University, Binzhou, People's Republic of China
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  • Xue Zhao,

    1. Department of Chemical Engineering and Materials Science, College of Chemistry, Shandong Normal University, Jinan, People's Republic of China
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  • Dezhan Chen

    Corresponding author
    1. Department of Chemical Engineering and Materials Science, College of Chemistry, Shandong Normal University, Jinan, People's Republic of China
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Abstract

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 H2 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. © 2014 Wiley Periodicals, Inc.

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