Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex

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Science  08 Mar 1996:
Vol. 271, Issue 5254, pp. 1397-1400
DOI: 10.1126/science.271.5254.1397


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-η22-O2)]2+ and [Cu2(μ-O)2]2+ cores through kinetic, spectroscopic, and crystallographic studies.