A dinuclear nickel peroxycarbonate complex: CO 2 addition promotes H 2 O 2 release.

Nickel coordination compounds featuring Ni-O bonds are key structural motifs in both bioinorganic and synthetic chemistries. They serve as precursors for organic substrate oxidation and are commonly invoked intermediates in water oxidation and oxygen reduction schemes. Herein, we disclose a series of well-defined dinuclear nickel complexes that, upon treatment with CO 2 and H 2 O 2 , afford the first nickel-bound peroxycarbonate. This unprecedented nickel-oxygen intermediate is stabilized by hydrogen bonding templated across the bimetallic core. Contrasting copper and iron analogues, the nickel peroxycarbonate reversibly dissociates H 2 O 2 , a process that is shown to be accelerated by exogenous CO 2 .