The chemistry of copper complexes with dioxygen will be explored, as it may relate to that in biological systems. Specific pursuits will include: 1) the synthesis of new ligands that are able to bind one, two, or three copper ions ligated by nitrogen atoms, preferably from the heterocycles pyridine or imidazole; 2) the incorporation of groups into such ligands that will influence the local copper ion environment by positioning a proton, an additional metal ion, a "substrate- binding cavity" or a non-polar hydrophobic moiety near the copper-binding site; 3) a study of the dioxygen, carbon monoxide, and anion-binding properties of such complexes; and 4) conducting oxidation reactions of organic molecules that associate with those ligands having a cavity by treating such complexes with dioxygen in the presence of substrate. In order to achieve these goals, use will be made of rigid organic molecules as ligand "anchors" that have the requisite stereochemical properties to bring the chosen groups into proximity, and the known dioxygen chemistry of pyridine- and imidazole-ligated copper complexes will be utilized as well. The organic frameworks comprise known and derivative triptindane and cavitand molecules that can be made in gram quantities from relatively simple starting materials. %%% In this project in the Inorganic, Bioinorganic, and Organo- metallic Program of the Chemistry Division, Dr. Thomas N. Sorrell of the University of North Carolina at Chapel Hill will explore the chemistry of copper complexes with dioxygen. The goal of these studies of model systems is to increase our knowledge of how copper-containing enzymes are able to catalyze metabolic and biosynthetic reactions.
