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High-valent metal-oxo species have been invoked as key intermediates in dioxygen O-O bond-cleavage and bond-formation reactions-for a number of metalloenzymes and synthetic catalysts. Manganese metalloenzymes, in particular, are involved in the activation and reduction of O2 (e.g. Mn ribonucleotide reductase and Mn lipoxygenase) and in mitigation of superoxide- and peroxide-induced damage (e.g. Mn-dependent superoxide dismutase and Mn catalase).