Nickel(ii) complexes with covalently attached quinols rely on ligand-derived redox couples to catalyze superoxide dismutation

Abstract

Although nickel is found in the active sites of a class of superoxide dismutase (SOD), nickel complexes with non-peptidic ligands normally do not catalyze superoxide degradation, and none has displayed activity comparable to those of the best manganese-containing SOD mimics. Here, we find that nickel complexes with polydentate quinol-containing ligands can exhibit catalytic activity comparable to those of the most efficient manganese-containing SOD mimics. The nickel complexes retain a significant portion of their activity in phosphate buffer and under operando conditions and rely on ligand-centered redox processes for catalysis. Although nickel SODs are known to cycle through Ni(II) and Ni(III) species during catalysis, cryo-mass spectrometry studies indicate that the nickel atoms in our catalysts remain in the +2 oxidation state throughout SOD mimicry.