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. 2011 Aug 5;333(6043):733-6.
doi: 10.1126/science.1206036.

A synthetic model of the Mn₃Ca subsite of the oxygen-evolving complex in photosystem II

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A synthetic model of the Mn₃Ca subsite of the oxygen-evolving complex in photosystem II

Jacob S Kanady et al. Science. .

Abstract

Within photosynthetic organisms, the oxygen-evolving complex (OEC) of photosystem II generates dioxygen from water using a catalytic Mn(4)CaO(n) cluster (n varies with the mechanism and nature of the intermediate). We report here the rational synthesis of a [Mn(3)CaO(4)](6+) cubane that structurally models the trimanganese-calcium-cubane subsite of the OEC. Structural and electrochemical comparison between Mn(3)CaO(4) and a related Mn(4)O(4) cubane alongside characterization of an intermediate calcium-manganese multinuclear complex reveals potential roles of calcium in facilitating high oxidation states at manganese and in the assembly of the biological cluster.

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