A Functional Model for O-O Bond Formation by the O 2 -Evolving Complex in Photosystem II

Author:

Limburg Julian1,Vrettos John S.1,Liable-Sands Louise M.2,Rheingold Arnold L.2,Crabtree Robert H.1,Brudvig Gary W.1

Affiliation:

1. Department of Chemistry, Yale University, Post Office Box 208107, New Haven, CT 06520–8107, USA.

2. Crystallography Laboratory, Department of Chemistry, University of Delaware, Newark, DE 19716, USA.

Abstract

The formation of molecular oxygen from water in photosynthesis is catalyzed by photosystem II at an active site containing four manganese ions that are arranged in di-μ-oxo dimanganese units (where μ is a bridging mode). The complex [H 2 O(terpy)Mn(O) 2 Mn(terpy)OH 2 ](NO 3 ) 3 (terpy is 2,2′:6′,2"-terpyridine), which was synthesized and structurally characterized, contains a di-μ-oxo manganese dimer and catalyzes the conversion of sodium hypochlorite to molecular oxygen. Oxygen-18 isotope labeling showed that water is the source of the oxygen atoms in the molecular oxygen evolved, and so this system is a functional model for photosynthetic water oxidation.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

Reference46 articles.

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2. Debus R. J., Biochim. Biophys. Acta 1102, 269 (1992);

3. ; B. A. Diner and G. T. Babcock in Oxygenic Photosynthesis: The Light Reactions vol. 4 of Advances in Photosynthesis D. R. Ort and C. F. Yocum Eds. (Kluwer Academic Dordrecht Netherlands 1996) pp. 214–240; R. D. Britt ibid. pp. 137–159.

4. Where Plants Make Oxygen: a Structural Model for the Photosynthetic Oxygen-Evolving Manganese Cluster

5. Manchanda R., Brudvig G. W., Crabtree R. H., Coord. Chem. Rev. 144, 1 (1995);

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