Mechanisms of Mn(V)-Oxo to Mn(IV)-Oxyl Conversion: From Closed-Cubane Photosystem II to Mn(V) Catalysts and the Role of the Entering Ligands
Publication Name
Chemistry - A European Journal
Abstract
The low activation barrier for O−O coupling in the closed-cubane Oxygen-Evolving Centre (OEC) of Photosystem II (PSII) requires water coordination with the Mn4 ′dangler′ ion in the Mn(V)-oxo fragment. This coordination transforms the Mn(V)-oxo complex into a more reactive Mn4(IV)-oxyl species, enhancing O−O coupling. This study explains the mechanism behind the coordination and indicates that in the most stable form of the OEC, the Mn4 fragment adopts a trigonal bipyramidal geometry but needs to transition to a square pyramidal form to be activated for O−O coupling. This transition stabilizes the Mn4 dxy orbital, enabling electron transfer from the oxo ligand to the dxy orbital, converting the oxo ligand into an oxyl species. The role of the water is to coordinate with the square pyramidal structure, reducing the energy gap between the oxo and oxyl forms, thereby lowering the activation energy for O−O coupling. This mechanism applies not only to the OEC system but also to other Mn(V)-based catalysts. For other catalysts, ligands such as OH− stabilize the Mn(IV)-oxyl species better than water, improving catalyst activation for reactions like C−H bond activation. This study is the first to explain the Mn(V)-oxo to Mn(IV)-oxyl conversion, providing a new foundation for Mn-based catalyst design.
Open Access Status
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