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How Does the Hemilabile Group in Ruthenium-Cp* Picolyl-NHC Complexes Affect the Mechanism of Transfer Hydrogenation Reaction? A DFT Study

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Abstract

The ruthenium-Cp* picolyl-NHC complexes catalyzed transfer hydrogenation reaction has been investigated with the aid of density functional theory calculations at the B3LYP level of theory. Two kinds of “hydridic route” (inner sphere mechanism) and one “direct hydrogen transfer route” (Meerwein–Ponndorf–Verley mechanism) have been examined. From the results we conclude that the stepwise inner sphere mechanism would be favored from the energetic point of view. The hemilability of the picolyl group plays an important role in determining which mechanism the transfer hydrogenation reaction should be followed. And the effect of agostic interaction has also been discussed.

Graphical Abstract

The ruthenium-Cp* picolyl-NHC complexes catalyzed transfer hydrogenation reaction has been investigated with the aid of density functional theory calculations at the B3LYP level of theory. Two kinds of “hydridic route” (inner sphere mechanism) and one “direct hydrogen transfer route” (Meerwein–Ponndorf–Verley mechanism) have been examined. From the results we conclude that the stepwise inner sphere mechanism would be favored from the energetic point of view. The hemilability of the picolyl group plays an important role in determining which mechanism the transfer hydrogenation reaction should be followed. And the effect of agostic interaction has also been discussed.

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Acknowledgments

Financial support for this research was granted by the Tianjin Natural Science Foundation (No. 14JCYBJC20100 X.X.), the MOE Innovation Team (No. IRT13022) of China, and the Natural Science Foundation of China (Project 21421001). The work was carried out at National Supercomputer Center in Tianjin, and the calculations were performed on TianHe-1(A). We thank to Professor Zunsheng Cai for his useful discussions and polishing of our manuscripts.

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  1. Department of Chemistry, Nankai University, Tianjin, 300071, People’s Republic of China

    Jie Ning, Zhenfeng Shang & Xiufang Xu

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  1. Jie Ning
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  2. Zhenfeng Shang
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  3. Xiufang Xu
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Correspondence to Zhenfeng Shang or Xiufang Xu.

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Ning, J., Shang, Z. & Xu, X. How Does the Hemilabile Group in Ruthenium-Cp* Picolyl-NHC Complexes Affect the Mechanism of Transfer Hydrogenation Reaction? A DFT Study. Catal Lett 145, 1331–1343 (2015). https://doi.org/10.1007/s10562-015-1524-5

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