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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Kanady et al. (2011) studied this question.
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