Understanding how water oxidation to molecular oxygen proceeds in molecular metal-oxo catalysts is a challenging endeavor due to their structural complexity. In this report, we unravel the water oxidation mechanism of the highly active water oxidation catalyst [Mn4V4O17(OAc)3]3-, a polyoxometalate catalyst with a [Mn4O4]6+ cubane core reminiscent of the natural oxygen-evolving complex. Starting from the activated species [Mn4 4+V4O17(OAc)2(H2O)(OH)]1-, we scrutinized multiple pathways to find that water oxidation proceeds via a sequential proton-coupled electron transfer (PCET), O-O bond formation, another PCET, an intramolecular electron transfer, and another PCET resulting in O2 evolution, with a predicted thermodynamic overpotential of 0.71 V. An in-depth investigation of the O-O bond formation process revealed an essential interplay between redox isomerism and Jahn-Teller effects, responsible for enhancing reactivity in the catalytic cycle. This is achieved by redistributing electrons between metal centers and weakening relevant bonds through Jahn-Teller distortions, introducing flexibility to the otherwise rigid cubane core of the catalyst. These mechanistic insights are expected to advance the design of efficient bioinspired Mn cubane water-splitting catalysts.
© 2021 The Authors. Published by American Chemical Society.