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

Jason A. Halfen, Samiran Mahapatra, Elizabeth C. Wilkinson, Susan Kaderli, Victor G. Young, Lawrence Que, Andreas D. Zuberbühler, William B. Tolman

Research output: Contribution to journalArticlepeer-review

433 Scopus citations

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

Original languageEnglish (US)
Pages (from-to)1397-1400
Number of pages4
JournalScience
Volume271
Issue number5254
DOIs
StatePublished - Mar 8 1996

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