Ligand Radical Mediated Water Oxidation by a Family of Copper o-Phenylene Bis-oxamidate Complexes

Understanding the reactivity landscape for the activation of water until the formation of the O-O bond and O-2 release in molecular chemistry is a decisive step in guiding the elaboration of cost-effective catalysts for the oxygen-evolving reaction (OER). Copper(II) complexes have recently caught the attention of chemists as catalysts for the 4e(-)/4H(+) water oxidation process. While a copper(IV) intermediate has been proposed as the reactive intermediate species, no spectroscopic signature has been reported so far. Copper(III) ligand radical species have also been formulated and supported by theoretical studies. We found, herein, that the reactivity sequence for the water oxidation with a family of Copper(II) o-phenylene bis-oxamidate complexes is a function of the substitution pattern on the periphery of the aromatic ring. In-situ EPR, FTIR, and rR spectroelectrochemical studies helped to sequence the elementary electrochemical and chemical events leading toward the O-2 formation selectively at the copper center. EPR and FTIR spectroelectrochemistry suggests that ligand-centered oxidations are preferred over metal-centered oxidations. rR spectroelectrochemical study revealed the accumulation of a bis-imine bound copper(II) superoxide species, as the reactive intermediate, under catalytic turnover, which provides the evidence for the O-O bond formation during OER.

Automated summary

By studying a series of Copper(II) complexes, it was found that the reactivity sequence depends on the substitution pattern around the aromatic ring, aiding in the understanding of the oxidation mechanism of water. In-situ spectroelectrochemical studies provided insights into the sequence of elementary electrochemical and chemical events leading to the formation of O-2, and the reactive intermediates involved in the reaction process were inferred.