Bis(imino)pyridine complex [Ni{2,6-(ArN=CMe)(2)C5H3N}Cl] (where Ar 2,6-(Pr2C6H3)-Pr-i) was synthesized by reduction of the corresponding dichloride complex and characterized as a Ligand-radical complex of Ni-II. Reaction of this complex with O-2 caused intraligand C-C bond cleavage to afford the Ni complex of the new iminoethylpyridylcarboxamidato ligand, which also was isolated as the corresponding carboxamide, 6-(ArN=CMe)C5H3N-2-C(O)NHAr. This reaction serves as an example of small-molecule activation effected directly at the redox-active bis(imino)pyridine ligand without an overall oxidation state change at the Ni center.