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A five-coordinate Mn(IV) intermediate in biological water oxidation: spectroscopic signature and a pivot mechanism for water binding
Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany..
Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany..
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2016 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 7, no 1, 72-84 p.Article in journal (Refereed) Published
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Abstract [en]

Among the four photo-driven transitions of the water-oxidizing tetramanganese-calcium cofactor of biological photosynthesis, the second-last step of the catalytic cycle, that is the S-2 to S-3 state transition, is the crucial step that poises the catalyst for the final O-O bond formation. This transition, whose intermediates are not yet fully understood, is a multi-step process that involves the redox-active tyrosine residue and includes oxidation and deprotonation of the catalytic cluster, as well as the binding of a water molecule. Spectroscopic data has the potential to shed light on the sequence of events that comprise this catalytic step, which still lacks a structural interpretation. In this work the S-2-S-3 state transition is studied and a key intermediate species is characterized: it contains a Mn3O4Ca cubane subunit linked to a five-coordinate Mn(IV) ion that adopts an approximately trigonal bipyramidal ligand field. It is shown using high-level density functional and multireference wave function calculations that this species accounts for the near-infrared absorption and electron paramagnetic resonance observations on metastable S-2-S-3 intermediates. The results confirm that deprotonation and Mn oxidation of the cofactor must precede the coordination of a water molecule, and lead to identification of a novel low-energy water binding mode that has important implications for the identity of the substrates in the mechanism of biological water oxidation.

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2016. Vol. 7, no 1, 72-84 p.
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Chemical Sciences
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URN: urn:nbn:se:uu:diva-274423DOI: 10.1039/c5sc03124aISI: 000366826900005OAI: oai:DiVA.org:uu-274423DiVA: diva2:896551
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationSwedish Energy Agency
Available from: 2016-01-21 Created: 2016-01-21 Last updated: 2017-11-30Bibliographically approved

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Mamedov, Fikret

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