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Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex
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 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 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, 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 (μ-η 2 :η 2 -O 2 )] 2+ and [Cu 2 (μ-O) 2 ] 2+ cores through kinetic, spectroscopic, and crystallographic studies.
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Citations
Cited by
Multicopper oxidases and oxygenases
Solomon, E. I., Sundaram, U. M., & Machonkin, T. E. (1996) · Chemical Reviews · doi:10.1021/cr950046o · Cited by 3,664
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis
Dau, H., Limberg, C., Reier, T., Risch, M., Roggan, S., & Strasser, P. (2010) · ChemCatChem · doi:10.1002/cctc.201000126 · Cited by 1,783
Oxygen Binding, Activation, and Reduction to Water by Copper Proteins
Solomon, E. I., Chen, P., Metz, M., Lee, S.-K., & Palmer, A. E. (2001) · Angewandte Chemie International Edition · doi:10.1002/1521-3773(20011217)40:24<4570::aid-anie4570>3.0.co;2-4 · Cited by 836
Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes
Wulfers, M. J., Teketel, S., Ipek, B., & Lobo, R. F. (2015) · Chemical Communications · doi:10.1039/c4cc09645b · Cited by 254
Metadata
- Authors
- Halfen, J. A., Mahapatra, S., Wilkinson, E. C., Kaderli, S., Young, V. G., Que, L., Zuberbühler, A. D., & Tolman, W. B.
- Venue
- Science
- Published
- 1996-03-08
- Volume
- 271
- Issue
- 5254
- Pages
- 1397-1400
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2112441679
- Cited by
- 545
- References
- 0
- FWCI
- 32.29
- Type
- journal article
- Language
- en
- Open access
- closed
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- Halfen, J. A., Mahapatra, S., Wilkinson, E. C., Kaderli, S., Young, V. G., Que, L., Zuberbühler, A. D., & Tolman, W. B. (1996). Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex. Science. https://doi.org/10.1126/science.271.5254.1397
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