Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex

Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with Mn^III tris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O₂ was generated at the Mn^V/IV potential with hydroxide, but a more anodic potential was required to evolve O₂ with only water. With a synthetic Mn^V(O) complex of 1, a second-order rate constant, k₂(OH^-), of 7.4 × 10³ M^-1 s^-1 was determined in the reaction of the Mn^V(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with a k₂(H₂O) value of 4.4 × 10^-3 M^-1 s^-1. This large reactivity difference of Mn^V(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a Mn^IV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex. Density functional theory calculations suggested that the nucleophilic attack of hydroxide on Mn^V(O) and also WNA to 1e^--oxidized Mn^V(O) are feasibly involved in the catalytic cycles but that direct WNA to Mn^V(O) is not likely to be the main O-O bond formation pathway in the electrocatalytic water oxidation by 1.