Application of N-donor ligated copper complexes in dioxygen activation and the synthesis of copper-sulfur clusters relevant to biology

Copper-containing proteins are essential to a wide variety of biological processes, with small molecule activation by copper centers being a ubiquitous theme in Nature. Dioxygen activation and nitrous oxide reduction are two of the most important and interesting examples of such processes. Our goal in the research presented here is to develop a better understanding of copper's role in both of these processes through the synthesis of small molecules that demonstrate reactivity and structural similarities to the biological systems, as well as to apply Nature's designs to developing potential oxidants from dioxygen or nitrous oxide.; Chapter 1 gives an overview of the biological and synthetic systems in which copper plays a role in either O2 or N2O activation, with particular emphasis on multicopper or copper-iron centers. Chapters 2 and 3 describe our efforts to synthesize and characterize heterobimetallic or "mixed-metal" oxo complexes containing copper with palladium, platinum, and germanium. Finally, Chapters 4 and 5 present an array of N-donor ligated copper-sulfide complexes we have synthesized and characterized. Many of these have surprising electronic structures, which provide insight into the fundamental nature of copper-sulfur bonding interactions that play important roles in the reduction of N2O by nitrous oxide reductase.