Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex
- 8 March 1996
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 271 (5254), 1397-1400
- https://doi.org/10.1126/science.271.5254.1397
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(μ-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(μ-O)2 cores. The viability of this notion has been demonstrated by the identification of an equilibrium between synthetic complexes having [Cu2(μ-η2:η2-O2)]2+ and [Cu2(μ-O)2]2+ cores through kinetic, spectroscopic, and crystallographic studies.Keywords
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