Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins
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...
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| Format: | Article |
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60729-x |
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| author | 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 Obadiah G. Reid |
| author_facet | 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 Obadiah G. Reid |
| author_sort | Max Kudisch |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-89c92e14144d4c46bd733b5a4f91a1c8 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-89c92e14144d4c46bd733b5a4f91a1c82025-08-20T03:45:34ZengNature PortfolioNature Communications2041-17232025-07-0116111110.1038/s41467-025-60729-xPhotolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling beginsMax Kudisch0Reagan X. Hooper1Lakshmy K. Valloli2Justin D. Earley3Anna Zieleniewska4Jin Yu5Stephen DiLuzio6Rebecca W. Smaha7Hannah Sayre8Xiaoyi Zhang9Matthew J. Bird10Amy A. Cordones11Garry Rumbles12Obadiah G. Reid13Chemistry and Nanoscience, National Renewable Energy LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryBrookhaven National LaboratoryChemistry and Nanoscience, National Renewable Energy LaboratoryChemistry and Nanoscience, National Renewable Energy LaboratoryAdvanced Photon Source, Argonne National LaboratoryDepartment of Chemistry and Chemical Biology, Northeastern UniversityMaterials Science, National Renewable Energy LaboratoryDepartment of Chemistry and Chemical Biology, Northeastern UniversityAdvanced Photon Source, Argonne National LaboratoryBrookhaven National LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryChemistry and Nanoscience, National Renewable Energy LaboratoryChemistry and Nanoscience, National Renewable Energy LaboratoryAbstract 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.https://doi.org/10.1038/s41467-025-60729-x |
| spellingShingle | 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 Obadiah G. Reid Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins Nature Communications |
| title | Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins |
| title_full | Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins |
| title_fullStr | Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins |
| title_full_unstemmed | Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins |
| title_short | Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins |
| title_sort | photolytic activation of ni ii x2l explains how ni mediated cross coupling begins |
| url | https://doi.org/10.1038/s41467-025-60729-x |
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