Investigation of the reactivity of molecular oxygen with copper(I) complexes is important in practical and biological settings, as for the first and then subsequent steps in dioxygen-activation for use in substrate oxidations/oxygenations, or for understanding elements in the copper ion mediated O2 reduction to water via four-electron four-proton chemistry. A primary research approach in our program in copper-dioxygen chemistry focuses on ligand design, systematic ligand variation and the use of cryogenic solution syntheses for the generation and investigation of new complexes. The ligand, in terms of first coordination sphere donor atom number and type, defines the structural, physical-spectroscopic and reaction properties of Cun/O2 complexes. In this presentation, recent results demonstrating the reactivity of (ligand)CuII-superoxo complexes toward C�H and O�H containing substrates will be described, in the context of copper enzymes which effect such reactions. Further, the reactivity toward proton and electron sources will be described for a different (ligand)CuII-superoxo complex, involving the reaction of the (ligand)Cu(II)-superoxo species to give a (ligand)CuII-hydroperoxo product. The relevance of the findings will also be discussed.

Copper(II)-superoxide complexes: Structure, substrate oxidations, and reduction-protonation chemistry

246th National Meeting (2013)

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