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Elucidating electron-transfer events in polypyridine nickel complexes for reductive coupling reactions

Nature Catalysis volume 6, pages 244–253 (2023)Cite this article

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Abstract

Polypyridine-ligated nickel complexes are widely used as privileged catalysts in a variety of cross-coupling reactions. The rapid adoption of these complexes is tentatively attributed to their ability to shuttle between different oxidation states and engage in electron-transfer reactions. However, these reactions are poorly understood in mechanistic terms. Here we investigate the reactivity of pseudohalide- and halide-ligated Ni(II) complexes, containing polypyridine ligands, in electron-transfer reactions. Specifically, Ni(II) halide complexes trigger comproportionation with Ni(0) with exceptional ease en route to Ni(I)Ln species, whereas the corresponding Ni(II) pseudohalide congeners are resistant to electron transfer, with Ni(I) pseudohalides being prone to disproportionation events. These observations are corroborated by electrochemical techniques and detailed quantum mechanical calculations. We also show that catalytically inactive Ni(II) pseudohalide complexes can be reactivated in the presence of exogeneous salts. From a broader perspective, this study provides rationalizations for overlooked and fundamental steps within the Ni-catalysed cross-coupling arena, thus offering blueprints for designing future Ni-catalysed reactions.

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Fig. 1: Ambiguity in electron transfer.
Fig. 2: Considerations for studying Ni polypyridine complexes.
Fig. 3: Effect of anonic ligands on electron transfer.
Fig. 4: Computational study of comproportionation.
Fig. 5: Electrochemical studies and stoichiometric reduction studies.
Fig. 6: Catalytic relevance of electron transfer.

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Data availability

Experimental procedures and characterization data for the stochiometric experiments, catalysts and the synthesized compounds along with computational information are included in the Supplementary Information. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: 3d (CCDC-2175355), 3c (CCDC-2175356), 3b (CCDC-2175354), 4a-Br (CCDC-2175353), 3a-Br (CCDC-2175357), [NiLi3Cl2(OtBu)3·2THF]2 (CCDC-2175358) and 3e (CCDC-2175352). Other data are available from the corresponding authors upon reasonable request.

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Acknowledgements

We thank ICIQ and FEDER/MCI−AEI/PGC2018-096839-B-I00 for financial support. C.S.D. thanks the European Union’s Horizon 2020 under the Marie Curie PREBIST grant agreement 754558. S.J.T. thanks Marie Sklodowska-Curie grant agreement No. 859910. O.G. thanks the NIGMS NIH (R35GM137797), the Camille and Henry Dreyfus Foundation and the Welch Foundation (A-2102-20220331) for funding and Texas A&M University HPRC resources (https://hprc.tamu.edu) for computational resources. We sincerely thank T. Skrydstrup for allowing revisions to be completed using his laboratory space and equipment, J. Benet for X-ray crystallographic data and G. Stoica for assistance with EPR experiments.

Author information

Author notes

  1. These authors contributed equally: Ángel Rentería-Gómez, Stephanie J. Ton, Achyut Ranjan Gogoi.

Authors and Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona, Spain

    Craig S. Day, Stephanie J. Ton & Ruben Martin

  2. Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, Tarragona, Spain

    Craig S. Day & Ruben Martin

  3. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Ángel Rentería-Gómez, Achyut Ranjan Gogoi & Osvaldo Gutierrez

  4. ICREA, Barcelona, Spain

    Ruben Martin

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Contributions

C.S.D. conceived the project. C.S.D. designed and performed the experimental studies unless otherwise stated. S.J.T. performed parts of the electrochemical experiments, stochiometric reductions and catalytic reactions. A.R.-G. and A.R.G. performed the computational studies. O.G. supervised the computational research. R.M. supervised the experimental research. C.S.D and R.M. prepared the initial manuscript. All authors contributed to discussions, commented on and edited the manuscript.

Corresponding authors

Correspondence to Osvaldo Gutierrez or Ruben Martin.

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Nature Catalysis thanks Behrouz Notash and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–75 and Tables 1–4.

Supplementary Data 1

Crystallographic data for compound 3d.

Supplementary Data 2

Crystallographic data for compound 3c.

Supplementary Data 3

Crystallographic data for compound 3b.

Supplementary Data 4

Crystallographic data for compound 4a-Br.

Supplementary Data 5

Crystallographic data for compound 3a-Br.

Supplementary Data 6

Crystallographic data for compound [NiLi3Cl2(OtBu)3·2THF]2.

Supplementary Data 7

Crystallographic data for compound 3e.

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Day, C.S., Rentería-Gómez, Á., Ton, S.J. et al. Elucidating electron-transfer events in polypyridine nickel complexes for reductive coupling reactions. Nat Catal 6, 244–253 (2023). https://doi.org/10.1038/s41929-023-00925-4

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