Copper(II)-superoxide complexes derive from the reaction of molecular oxygen with reduced copper(I) compounds.  Their structures and properties are of fundamental interest as well as their subsequent reactivity toward substrates. These subjects impact on practical applications and on the utilization of dioxygen in biological systems. A primary research approach in our program in copper-dioxygen chemistry focuses on ligand design, systematic ligand variation and the use of cryogenic solution handling for the generation and investigation of new complexes. The ligand first coordination sphere donor atom number and type, defines the structural, physical-spectroscopic and reaction properties of Cun/O2 complexes. In the context of copper enzymes which effect such reactions. we will present recent results demonstrating the reactivity of (ligand)CuII-superoxo complexes of differing identity toward (a) C�H and O�H containing substrates, (b) reduction-protonation employing redox reagents and protic acids and (c) reversible reduction of a superoxo- to a peroxo-dicopper(II) compound. The effect of replacing a nitrogen donor atom with a thioether group, within a chelating tetradentate ligand, will be discussed in terms of reactivity differences and possible biochemical relevance.

Ligand effects on the formation, structure, and reactivity of primary copper-dioxygen adducts

248th National Meeting (2014)

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