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Ruthenium [NNN] and [NCN]-type pincer complexes with phosphine coligands: synthesis, structures and catalytic applications

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Abstract

A series of ruthenium [NNN]- or [NCN]-type complexes (3–7) bearing PPh3 ancillary ligands have been synthesized from pyridine- or phenylene-bridged bis(triazoles) 1 and 2. In the case of [NNN]-pincer complex 3, an unusual and unexpected cis-orientation adopted by two sterically demanding PPh3 ligands was observed, and such configuration proved to be unchanged in solution for a long time. By contrast and as expected, the two phosphines are found to be trans to each other in the case of [NCN]-type pincer complex 4, but an oxidation of RuII center to RuIII occurred. Complex cis-3 underwent ligand exchanges leading to the formations of diphosphine derivatives 5 and 6. As a representative, cis-3 was treated with the base in isopropanol affording a mixture of Ru–hydrido complexes with various phosphine binding modes, one of which (trans-7) bearing two trans-standing phosphines has been successfully isolated and fully characterized. The catalytic performances of all newly synthesized Ru complexes have been examined and compared in transfer hydrogenations of ketones and enones, in which mono-phosphine complexes proved to be significantly superior to their diphosphine counterparts. The catalytic process proved to involve Ru–H key intermediates, but the trans-oriented Ru–H species is unlikely to be the main catalytic contributor. In particular, the best performer cis-3 exhibits high chemoselectivity in certain cases catalyzing α,β-unsaturated ketones, whose behavior is quite different compared to most precedents.

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Notes

  1. For a related review, see [1].

  2. For selected reviews, see [2,3,4,5,6].

  3. For recent papers focusing on the Ru–btp complexes and their photoluminescence applications, see [7,8,9].

  4. For selected reviews on Ru pincer complexes, see [10,11,12,13].

  5. For selected examples, see [14,15,16,17,18,19,20].

  6. For selected examples, see [20,21,22,23,24,25,26,27].

  7. To the best of our knowledge, there is only one report regarding Ru NNN pincer complexes bearing two cis-standing mono-phosphines. For this paper, see Ref. [15].

  8. For the report in which the term “transphobia effect” was coined, see [32].

  9. For a review, see [33].

  10. For selected reviews on TH reactions, see [39,40,41,42,43].

  11. For a review on Ru-mediated THs of enones, see [44,45,46,47,48].

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Acknowledgements

The authors thank “General Project of Scientific Research Program of Beijing Education Commission” (Grant No. KM201810028007), National Natural Science Foundation of China (Grant No. 21502122) and Beijing Natural Science Foundation (Grant No. 2192012) for financial support. The author Dr. Shuai Guo also highly appreciates the support from Yenching Young Scholar Cultivation Program of Capital Normal University.

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Authors and Affiliations

  1. Department of Chemistry, Capital Normal University, Beijing, People’s Republic of China

    Bo Zhang, Haiying Wang, Xuechao Yan, Yu-Ai Duan & Shuai Guo

  2. College of Life and Environment Science, Minzu University of China, Beijing, People’s Republic of China

    Fei-Xian Luo

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  1. Bo Zhang
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Zhang, B., Wang, H., Yan, X. et al. Ruthenium [NNN] and [NCN]-type pincer complexes with phosphine coligands: synthesis, structures and catalytic applications. Transit Met Chem 45, 99–110 (2020). https://doi.org/10.1007/s11243-019-00362-y

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