Inspired by a diverse array of copper ion mediated “O2-activation” processes occurring in synthetic catalysis or at the active-sites of copper proteins, our research program has focused on fundamentally important and potentially applicable copper-dioxygen chemistry and oxidative reactivity. The broad program has emphasized (a) ligand design and the development of new copper(I) chemistry, (b) the determination of the kinetics-thermodynamics of CuIn/O2 (n = 1, 2) adduct formation, (c) for superoxide, (hydro)peroxide or oxy species, elucidation of Cu/oxygen-atom connectivity, coordination geometry, correlation to spectroscopic properties along with electronic structure elucidation and (d) explication of subsequent reactivity patterns for the species which can be characterized. In fact, these properties depend heavily upon the nature of the multidentate ligand employed, as it defines the coordination number, geometry and all resulting properties. A complementary program in heme/copper/O2 reactivity also developed, inspired by the presence of such biological hetero-binuclear centers involved in O2-binding and four-electron reduction. Further, such investigations have also required explorations of heme-only chemistry, O2 and reduced derivative complexes which also are relevant to heme oxidation-oxygenation catalysts and/or the large array of heme enzymes occurring in nature. In this lecture, a focus will be placed on overviews of past research, along with a detailing of most recent projects in copper and/or heme bioinorganic dioxygen chemistry.

Ligand-copper and porphyrinate-iron coordination complexes with molecular oxygen and its reduced derivatives

ACS Spring Meeting 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.