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  A five-coordinate Mn(IV) intermediate in biological water oxidation: spectroscopic signature and a pivot mechanism for water binding

Retegan, M., Krewald, V., Mamedov, F., Neese, F., Lubitz, W., Cox, N., et al. (2016). A five-coordinate Mn(IV) intermediate in biological water oxidation: spectroscopic signature and a pivot mechanism for water binding. Chemical Science, 7(1), 72-84. doi:10.1039/C5SC03124A.

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 Creators:
Retegan, Marius1, Author              
Krewald, Vera1, Author              
Mamedov, Fikret2, Author
Neese, Frank1, Author              
Lubitz, Wolfgang3, Author              
Cox, Nicholas3, Author              
Pantazis, Dimitrios A.1, Author              
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Molecular Biomimetics, Department of Chemistry – Ångstrom Laboratory, Uppsala University, Box 523, 75120 Uppsala, Sweden, ou_persistent22              
3Research Department Lubitz, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023873              

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 Abstract: 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 S2 to S3 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 S2–S3 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 S2–S3 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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Language(s): eng - English
 Dates: 2015-08-222015-11-172016-01-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C5SC03124A
 Degree: -

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Title: Chemical Science
  Other : Chem. Sci.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 7 (1) Sequence Number: - Start / End Page: 72 - 84 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520