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Science. 1996 Mar 8;271(5254):1397-400.

Reversible cleavage and formation of the dioxygen O-O bond within a dicopper complex.

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  • 1Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.

Abstract

A key step in dioxygen evolution during photosynthesis is the oxidative generation of the O-O bond from water by a manganese cluster consisting of M2(mu-O)2 units (where M is manganese). The reverse reaction, reductive cleavage of the dioxygen O-O bond, is performed at a variety of dicopper and di-iron active sites in enzymes that catalyze important organic oxidations. Both processes can be envisioned to involve the interconversion of dimetal-dioxygen adducts, M2(O2), and isomers having M2(mu-O)2 cores. The viability of this notion has been demonstrated by the identification of an equilibrium between synthetic complexes having [Cu2(mu-eta2:eta2-O2)]2+ and [Cu2(mu-O)2]2+ cores through kinetic, spectroscopic, and crystallographic studies.

PMID:
8596910
[PubMed - indexed for MEDLINE]
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