| Chapters 1 and 2 describe in detail the O2-binding chemistry of (F8TPP)FeII and (6L)Fe II, which yields heme-superoxo {lcub}PFeIII-(O2 −){rcub} and heme-peroxo-heme {lcub}(PFeIII)2-(O 22−){rcub} dioxygen adducts, as deduced by multi-nuclear (1H, 2H, 19F) magnetic resonance (NMR) and UV-visible spectroscopies, and dioxygen-uptake methodologies. We also describe the spectroscopic features of (B)(F8TPP)Fe IV = O (B = base), a ferryl-oxo complex. These studies employing mononuclear heme-only complexes form the foundation for understanding the dioxygen reactivity of the heterobinuclear heme/Cu systems as models for the active site of cytochrome c oxidase.; In Chapters 3 and 4, we present the dioxygen reactivity of a simple 1:1 mixture of (F8TPP)FeII and [(TMPA)CuI(MeCN)] +, and of [(6L)FeIICuI] +, respectively, both of which form high-spin heme-peroxo Cu complexes, [PFeIII-(O22−)-CuII ]+, as revealed by low-temperature spectral investigations (UV-visible, resonance Raman, NMR, Mössbauer, and EPR spectroscopies), dioxygen-uptake studies, stopped flow kinetics, and mass spectrometry. EXAFS spectroscopy suggests the presence of a μ-1,2 peroxo ligand. Thermal decomposition of these heme-peroxo-Cu complexes yields μ-oxo heme-Cu complexes, PFe III-O-CuII, with concomitant liberation of a half-equivalent of O2.; The focus of Chapter 5 is on the modeling of copper-cluster containing metalloenzymes. Thus, we have structurally characterized tricopper complexes employing mesitylene-based trinucleating ligands. Furthermore, a new series of more structured cyclotriveratrilene ligands were also designed, synthesized and characterized. |
