The electronic structures of nickel and cobalt centers coordinated by two α-iminoketone ligands have been elucidated using density functional theory calculations and a host of physical methods such as X-ray crystallography, cyclic voltammetry, UV-vis spectroscopy, electron paramagnetic resonance spectroscopy, and magnetic susceptibility measurements. In principle, α-iminoketone ligands can exist in three oxidation levels: the closed-shell neutral form (L)0, the closed-shell dianion (L red)2-, and the open-shell monoanion (L •)-. Herein, the monoanionic π-radical form (L•)- of α-iminoketones is characterized in the compounds [(L•)2Ni] (1) and [(L•) 2Co] (3), where (L•)- is the one-electron-reduced form of the neutral ligand (t-Bu)N=CH-C(Ph)=O. The metal centers in 1 and 3 are divalent, high-spin, and coupled antiferromagnetically to two ligand π radicals. These bis(ligand)metal complexes can be chemically oxidized by two electrons to give the dications [trans-(L)2Ni(CH 3CN)2](PF6)2 (2) and [trans-(L) 2Co(CH3-CN)2](PF6)2 (4), wherein the ligands are in the neutral form.