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 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(sp(3)) electrophiles in cross-coupling reactions.