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

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. Cordones, Garry Rumbles and Obadiah G. Reid ()
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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
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
Xiaoyi Zhang: Argonne National Laboratory
Matthew J. Bird: Brookhaven National Laboratory
Amy A. Cordones: SLAC National Accelerator Laboratory
Garry Rumbles: National Renewable Energy Laboratory
Obadiah G. Reid: National Renewable Energy Laboratory

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: 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.

Date: 2025
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DOI: 10.1038/s41467-025-60729-x

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