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Understanding of Co(I)-Catalyzed Hydrogenation of C=C and C=O Substrates

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Abstract

The first-row transition metal catalysis often serves as a complementary strategy to traditional precious metal catalysis. Other than their advantages in abundance and sustainability, their unique electronic properties often give rise to more complicated reactivities. Co-catalyzed hydrogenation is an example of these relatively underexplored first-row transition metal catalysis. In this work, we will focus on an example of Co-catalyzed hydrogenation, which was reported to be able to selectively hydrogenate C=C but not C=O. We have performed DFT calculations on the model reactions, accompanied by a series of structure and bonding analysis, to investigate the underlying reason for the observed selectivity. We have identified the predominant σ-donating nature of phosphine and the π-accepting nature of C=C/C=O fragments upon interaction with Co(I) center, and we have also analyzed why these differences would lead to different coordination geometry, stability, and reactivity. We anticipate that all these analyses would advance our understanding in Co(I) catalysis and are beneficial for future Co-based catalyst design.

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Acknowledgements

This work is supported by the Research Grants Council of Hong Kong (HKUST 16305119 and 16300620). The authors thank Miss Xueying Guo for her help on preparing the manuscript, Dr. Jing-Xuan Zhang and Dr. Zhihan Zhang (alumni of the Lin group in HKUST) for their valuable discussions.

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Authors and Affiliations

  1. Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China

    Tilong Yang, Fu Kit Sheong & Zhenyang Lin

  2. Institute for Advanced Study, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China

    Fu Kit Sheong

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  1. Tilong Yang
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Correspondence to Fu Kit Sheong or Zhenyang Lin.

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Yang, T., Sheong, F.K. & Lin, Z. Understanding of Co(I)-Catalyzed Hydrogenation of C=C and C=O Substrates. Top Catal 65, 472–480 (2022). https://doi.org/10.1007/s11244-021-01481-6

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