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The present volume is a description of the current knowledge on the different metal-oxo and metal-peroxo species which are involved in catalytic oxidations. These highly reactivity metal-oxygen species are the key intermediates in heme or non-heme oxygenases, as well as in metal-catalyzed oxidations. The accumulated knowledge on these reactive entities will facilitate a better understanding of the different intermediates involved in the catalytic cycles of enzymes like cytochromes P-450, non-heme oxygenases, copper oxygenases, in the oxidation of water by the manganese-center of Photosystem II, in the chemistry of dioxiranes and also in DNA cleavage performed by activated bleomycin. The description of these metal-oxo and metal-peroxo species is based on physico-chemical data, reactivity results and also on theoretical calculations.
List of contents
Active Iron-Oxo and Iron-Peroxo Species in Cytochromes P450 and Peroxidases; Oxo-Hydroxo Tautomerism with Water-Soluble Metalloporphyrins.- Nucleophilicity of Iron-Peroxo Porphyrin Complexes.- Characterization of High-Valent Oxo-Metalloporphyrins.- Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase.- Quantum Chemical Studies on Metal-Oxo Species Related to the Mechanisms of Methane Monooxygenase and Photosynthetic Oxygen Evolution.- Characterization and Properties of Non-Heme Iron Peroxo Complexes.- Copper-Dioxygen and Copper-Oxo Species Relevant to Copper Oxygenases and Oxidases.- Rhenium-Oxo and Rhenium-Peroxo Complexes in Catalytic Oxidations.- Structure, Reactivity, and Selectivity of Metal-Peroxo Complexes Versus Dioxiranes.- Nature of Activated Bleomycin.
