Redox Activity of Pyridine-Oxazoline Ligands in the Stabilization of Low-Valent Organonickel Radical Complexes

Low-valent organonickel radical complexes are common intermediates in cross-coupling reactions and metalloenzyme-mediated processes. The electronic structures of N-ligand supported nickel complexes appear to vary depending on the actor ligands and the coordination number. The reduction products of a...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-04, Vol.143 (14), p.5295-5300
Main Authors: Wagner, Clifton L, Herrera, Gabriel, Lin, Qiao, Hu, Chunhua T, Diao, Tianning
Format: Article
Language:English
Subjects:
Coordination Complexes - chemistry
Free Radicals - chemistry
Ligands
Models, Molecular
Molecular Structure
Nickel - chemistry
Oxazoles - chemistry
Oxidation-Reduction
Pyridines - chemistry
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Summary:Low-valent organonickel radical complexes are common intermediates in cross-coupling reactions and metalloenzyme-mediated processes. The electronic structures of N-ligand supported nickel complexes appear to vary depending on the actor ligands and the coordination number. The reduction products of a series of divalent (pyrox)Ni complexes establish the redox activity of pyrox in stabilizing electron-rich Ni­(II)–alkyl and −aryl complexes by adopting a ligand-centered radical configuration. The reduced pyrox imparts an enhanced trans-influence. In contrast, such redox activity was not observed in a (pyrox)­Ni­(I)–bromide species. The excellent capability of pyrox in stabilizing electron-rich Ni species resonates with its proclivity in promoting the reductive activation of C­(sp3) electrophiles in cross-coupling reactions.
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.1c00440