This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. Primary support for the subproject and the subproject's principal investigator may have been provided by other sources, including other NIH sources. The Total Cost listed for the subproject likely represents the estimated amount of Center infrastructure utilized by the subproject, not direct funding provided by the NCRR grant to the subproject or subproject staff. Copper enzymes exhibit a range of reactivities with dioxygen and the use of small-molecule models offers a means of probing enzyme mechanism in a detailed and systematic manner. The cooperativity of transition metal ions and pro-radical ligands in metalloenzyme active sites is of current research interest. One such example, Galactose oxidase (GOase), is a mononuclear copper enzyme that catalyzes the aerobic oxidation of primary alcohols. In an effort to understand the intricacies of the interaction of Cu with organic radicals, a series of Schiff-base (salen), half-reduced-salen, and fully reduced-salen Cu(II) complexes and their one-electron oxidized form have been prepared. By tuning the electronic properties of these planar ligands we aim to develop a deeper understanding of the factors that govern the oxidation locus in their one-electron oxidized forms. Depending on the relative energies of the redox-active orbitals, metal complexes with pro-radical ligands can exist in two limiting electronic forms: a metal-ligand radical (Mn+(L?)) or a high valent metal complex (M(n+1)+(L-)). In the case of the oxidized Cu-salen complexes, Cu(III)-phenolate or Cu(II)-phenoxyl radical species are possible, which can potentially exist in a valence tautomeric equilibrium through variation of the ligand field and/or temperature. XAS investigations will provide information on the locus of oxidation of these complexes, and the electronic factors that stabilize one or the other of these reactive forms. XAS is an especially useful technique for this work, as it is specifically sensitive to the metal oxidation state, and as it provides a means for understanding how geometric and electronic structure interact (via analysis of K-edge, EXAFS, and L-edge). The work proposed in this study addresses bioinorganic questions as well as several more fundamental chemical and spectroscopic issues.
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