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Mechanistic insights into small molecule activation induced by ligand cooperativity in PCcarbeneP nickel pincer complexes: a quantum chemistry study

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Abstract

Mechanisms for the activation of water, ammonia, and other small molecules by the PCcarbeneP nickel pincer complex were studied computationally with the aid of density functional theory. The calculation results indicate that the strongly donating, nucleophilic carbene center can engage in a variety of heterolytic splitting of E−H (E=H, C, N, O) bonds, some of which are reversible. The cleavage of E−H bonds across the Ni=C bond represents a new mode of bond activation by ligand cooperativity in nickel pincer complex. On the basis of the calculations, we also demonstrate that reversible H2 activation across the Ir=C bond via the PCcarbeneP iridium pincer complex was observed in the experiments, while other E−H (E=C, N, O) bonds were not activated. Our calculations are in good agreement with experimental observations and could provide new insights into ligand cooperativity in nickel pincer complexes.

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Acknowledgments

This work was supported by the National Science Foundation of China (21203166, 21473157), the Natural Science Foundation of Zhejiang Province (Y4100620), and the Food Science and Engineering the Most Important Discipline of Zhejiang Province (JYTsp2014111). We thank the State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University) for providing computational resources.

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Authors and Affiliations

  1. Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou, 310018, China

    Cheng-Cheng Liu, Qing-Lan Liu, Zun-Yi Wu, Ya-Cui Chen & Hu-Jun Xie

  2. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Qun-Fang Lei & Wen-Jun Fang

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  1. Cheng-Cheng Liu
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  2. Qing-Lan Liu
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Correspondence to Hu-Jun Xie.

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Liu, CC., Liu, QL., Wu, ZY. et al. Mechanistic insights into small molecule activation induced by ligand cooperativity in PCcarbeneP nickel pincer complexes: a quantum chemistry study. J Mol Model 21, 242 (2015). https://doi.org/10.1007/s00894-015-2792-0

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