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Deciphering the mechanism of the Ni-photocatalyzed C‒O cross-coupling reaction using a tridentate pyridinophane ligand

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  • Hanah Na

    (University of Illinois at Urbana-Champaign)

  • Liviu M. Mirica

    (University of Illinois at Urbana-Champaign)

Abstract

Photoredox nickel catalysis has emerged as a powerful strategy for cross-coupling reactions. Although the involvement of paramagnetic Ni(I)/Ni(III) species as active intermediates in the catalytic cycle has been proposed, a thorough spectroscopic investigation of these species is lacking. Herein, we report the tridentate pyridinophane ligands RN3 that allow for detailed mechanistic studies of the photocatalytic C–O coupling reaction. The derived (RN3)Ni complexes are active catalysts under mild conditions and without an additional photocatalyst. We also provide direct evidence for the key steps involving paramagnetic Ni species in the proposed catalytic cycle: the oxidative addition of an aryl halide to a Ni(I) species, the ligand exchange/transmetalation at a Ni(III) center, and the C–O reductive elimination from a Ni(III) species. Overall, the present work suggests the RN3 ligands are a practical platform for mechanistic studies of Ni-catalyzed reactions and for the development of new catalytic applications.

Suggested Citation

  • Hanah Na & Liviu M. Mirica, 2022. "Deciphering the mechanism of the Ni-photocatalyzed C‒O cross-coupling reaction using a tridentate pyridinophane ligand," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28948-8
    DOI: 10.1038/s41467-022-28948-8
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    References listed on IDEAS

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    1. Jack A. Terrett & James D. Cuthbertson & Valerie W. Shurtleff & David W. C. MacMillan, 2015. "Switching on elusive organometallic mechanisms with photoredox catalysis," Nature, Nature, vol. 524(7565), pages 330-334, August.
    2. John F. Hartwig, 2008. "Carbon–heteroatom bond formation catalysed by organometallic complexes," Nature, Nature, vol. 455(7211), pages 314-322, September.
    3. Sean H. Kennedy & Balu D. Dherange & Kathleen J. Berger & Mark D. Levin, 2021. "Skeletal editing through direct nitrogen deletion of secondary amines," Nature, Nature, vol. 593(7858), pages 223-227, May.
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