The monoanionic pi-radical redox state of alpha-iminoketones in bis(ligand)metal complexes of nickel and cobalt

The electronic structures of nickel and cobalt centers coordinated by two alpha-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, alpha-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 pi-radical form (L*)(-) of alpha-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 pi radicals. These bis(ligand)metal complexes can be chemically oxidized by two electrons to give the dications trans-(L)2Ni(CH3CN)2](PF6)2 (2) and trans-(L)2Co(CH3CN)2](PF6)2 (4), wherein the ligands are in the neutral form.