Mononuclear copper(I)-dioxygen adducts possessing nitrogen-containing chelating ligands can be best described as cupric-superoxide complexes. Such initial complexes are also found in copper enzymes where they either attack a substrate or are protonated-reduced. Thus, the structures, physical properties and reactivity toward protons-electrons and-or substrates are of fundamental interest in chemicals systems where O2-reduction occurs (e,g,, in fuel cells), and where organic substrates are oxidized or oxygenated. Our primary research approach in copper-dioxygen chemistry focuses on ligand design and variation and the use of cryogenic solution handling for the study of new complexes. In these contexts, a description of new (ligand)Cu(II)-superoxo complexes will be presented, those which can effect the oxidation of C–H and O–H containing substrates, or those undergoing reduction-protonation and/or (c) those where reversible reduction of a superoxo- to a peroxo-dicopper(II) occurs. The latter employ binucleating ligands where two copper ions in close proximity possess an O(phenolate) ligand donor; a mixed-valent Cu(I)Cu(II) precursor reacts reversibly to form a superoxo-dicopper(II) product which can be reversibly reduced to a peroxo-dicopper(II) analogue. Following titrations using a series of oxidants/reductants, a redox potential and lamda value (reorganization energy) for the peroxide/superoxide complex pair transformations can be derived.  Progress toward the generation and study of biomimetic mononuclear cupric superoxo complexes possessing a thioether ligand-donor or H-bonding moieties will also be presented.<br/>

Progress in the generation and characterization of primary copper(I)-dioxygen adducts

251st National Meeting (2016)

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