A computational investigation of the hydrogenation of imines catalyzed by rhodium thiolate complexes
Article first published online: 22 AUG 2014
© 2014 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Volume 115, Issue 1, pages 1–5, January 5, 2015
How to Cite
How to cite this article: J. Quantum Chem. 2015, 114, 1–5. 10.1002/qua.24751., , .
- Issue published online: 19 NOV 2014
- Article first published online: 22 AUG 2014
- Manuscript Accepted: 5 AUG 2014
- Manuscript Revised: 1 AUG 2014
- Manuscript Received: 26 MAY 2014
- National Natural Science Foundations of China . Grant Number: 21375082
- Scientific Research Fund of Binzhou University . Grant Number: 2010Y04
- Binzhou Science and Technology Development Plan . Grant Number: 2013ZC0703
- rhodium thiolate complexes;
- catalytic mechanism;
- density functional theory
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.