Flexibility Enhances Reactivity: Redox Isomerism and Jahn-Teller Effects in a Bioinspired Mn₄O₄ Cubane Water Oxidation Catalyst.

ABSTRACT: 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 intramolecul

SUBMITTER: Schwiedrzik L 

PROVIDER: S-EPMC8576808 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature