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Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex
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 M$_2$(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 dicoipper an...
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Published in: | Science (American Association for the Advancement of Science) 1996-03, Vol.271 (5254), p.1397-1400 |
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Main Authors: | , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | 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 M$_2$(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 dicoipper 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, M$_2$(O$_2$), and isomers having M$_2$(μ-O)$_2$ cores. The viability of this notion has been demonstrated by the identification of an equilibrium between synthetic complexes having [Cu$_2$($\mu - \eta^2$: $\eta^2 -O_2$)]$^{2+}$ and [cu$_2$(μ-O)$_2$]$^{2+}$ cores through kinetic, spectroscopic, and crystallographic studies. |
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ISSN: | 0036-8075 1095-9203 |
DOI: | 10.1126/science.271.5254.1397 |