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Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins

Author

Listed:
  • Max Kudisch

    (National Renewable Energy Laboratory)

  • Reagan X. Hooper

    (SLAC National Accelerator Laboratory)

  • Lakshmy K. Valloli

    (Brookhaven National Laboratory)

  • Justin D. Earley

    (National Renewable Energy Laboratory
    University of Colorado, Boulder)

  • Anna Zieleniewska

    (National Renewable Energy Laboratory)

  • Jin Yu

    (Argonne National Laboratory)

  • Stephen DiLuzio

    (Northeastern University)

  • Rebecca W. Smaha

    (National Renewable Energy Laboratory)

  • Hannah Sayre

    (Northeastern University
    Northeastern University)

  • Xiaoyi Zhang

    (Argonne National Laboratory)

  • Matthew J. Bird

    (Brookhaven National Laboratory)

  • Amy A. Cordones

    (SLAC National Accelerator Laboratory)

  • Garry Rumbles

    (National Renewable Energy Laboratory
    University of Colorado, Boulder
    University of Colorado, Boulder)

  • Obadiah G. Reid

    (National Renewable Energy Laboratory
    University of Colorado, Boulder)

Abstract

Nickel photocatalysis has recently become vital to organic synthesis, but how the Ni(II)X2L pre-catalyst (X = Cl, Br; L = bidentate ligand) becomes activated to Ni(I)XL has remained puzzling and is typically addressed on a case-by-case basis. Here, we reveal a general mechanism where light induces photolysis of the Ni(II)-X bond, either via direct excitation or triplet energy transfer. Photolysis produces Ni(I)XL and a halogen radical, X•. Subsequent hydrogen atom abstraction, often from the solvent, produces a C(sp3) radical, R•, that recombines with Ni(I) to form organonickel(II) complexes, Ni(II)XRL. Rather than acting as a loss pathway, Ni(II)XRL behaves as a light-activated reservoir of Ni(I) via photolysis of the Ni(II)-C bond. These results explain the role of the solvent in protecting the catalyst from off-cycle dimerization, demonstrate that two photons are often required to drive the reaction, and show how tuning the ligand can control the concentration of active Ni(I) species.

Suggested Citation

  • Max Kudisch & Reagan X. Hooper & Lakshmy K. Valloli & Justin D. Earley & Anna Zieleniewska & Jin Yu & Stephen DiLuzio & Rebecca W. Smaha & Hannah Sayre & Xiaoyi Zhang & Matthew J. Bird & Amy A. Cordon, 2025. "Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-60729-x
    DOI: 10.1038/s41467-025-60729-x
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    References listed on IDEAS

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    1. Rajesh Kancherla & Krishnamoorthy Muralirajan & Bholanath Maity & Safakath Karuthedath & Gadde Sathish Kumar & Frédéric Laquai & Luigi Cavallo & Magnus Rueping, 2022. "Mechanistic insights into photochemical nickel-catalyzed cross-couplings enabled by energy transfer," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. 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.
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