Journal
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
Volume 9, Issue 6, Pages 669-683Publisher
SPRINGER
DOI: 10.1007/s00775-004-0578-4
Keywords
bis-mu-oxo complexes; copper-dioxgen complexes; hydroperoxo complexes; peroxo complexes; side-on bonding
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The considerable recent advances in copper-dioxygen coordination chemistry demonstrate the existence of a variety of dioxygen-derived Cu-n-O-2 complexes, forming a basis for discussion of alternate oxidant types in copper chemistry and biochemistry. Peroxo complexes may react as nucleophilic reagents, and several types of electrophilic mono- or dicopper (hydro)peroxides exist. Side-on peroxo-dicopper(II) species effect aromatic hydroxylations, including phenolic substrates, in model systems and in the enzyme tyrosinase. Bis-mu-oxo-dicopper(III) entities are capable of hydrogen-atom abstraction reactions, or atom transfer to phosphines and sulfides. The scope and mechanisms of mononuclear Cu(II) superoxides or peroxides are yet to be established, but may be relevant to monooxygenases like peptidylglycine alpha-hydroxylating monooxygenase.
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