Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation

Nicholas Cox*, Marius Retegan, Frank Neese, Dimitrios A. Pantazis, Alain Boussac, Wolfgang Lubitz

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

416 Citations (Scopus)

Abstract

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived fromquantum chemicalmodeling is consistentwith allmagnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximalmanganese-bound oxygens in the transition state of the cofactor.

Original languageEnglish
Pages (from-to)804-808
Number of pages5
JournalScience
Volume345
Issue number6198
DOIs
Publication statusPublished - 15 Aug 2014
Externally publishedYes

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