Jackson, Timothy ALeto, Domenick F.2017-01-082017-01-082014-08-312014http://dissertations.umi.com/ku:13532https://hdl.handle.net/1808/22548Manganese centers that react with O2 and its reduced derivatives mediate a diverse array of biologically important reactions including the detoxification of superoxide, the conversion of nucleotides to deoxynucleotides, and the generation of O2 from H2O. Peroxo-, oxo-, and hydroxo-manganese motifs are frequently invoked in the catalytic cycles of Mn enzymes. To that end, biomimetic complexes featuring peroxo-, oxo-, and hydroxo-manganese adducts were synthesized and studied using spectroscopic techniques, including variable-temperature electronic absorption, electron paramagnetic resonance (EPR), X-ray absorption (XAS), and magnetic circular dichroism (MCD) spectroscopies along with computational methods, such as density functional theory (DFT) and time-dependent DFT. The structural and spectroscopic properties of these species were investigated in order to better understand how the geometric and electronic structure of these complexes affects reactivity.296 pagesenCopyright held by the author.ChemistrybiomimeticManganeseoxoperoxoreactivityspectroscopyDissertationopenAccess