摘要：

This thesis describes the synthesis, characterization and reactivity of metal-triazacorrole complexes. There has been much interest in the field of corrole chemistry, specifically high-valent metallocorroles. Corroles are similar to porphyrins but are missing one meso-carbon and have a direct Calpha-Calpha bond. We have studied these compounds for their ability to stabilize high-valent metals while at the same time being reactive towards various substrates. From these compounds we may better understand transition states found in biological systems and also new and exciting synthetic applications.; Chapter 1 reviews the porphyrinioid class of compounds. The discussion includes the biological basis for studying corrolazines, recent reactivity of corroles and progress made in corrolazine chemistry. High-valent metal-oxo reactivity is a major focus of this chapter. The goals of this project are outlined in detail.; In Chapter 2, there is a discussion about the synthesis, characterization and physicochemical properties of manganese(III) and manganese(V)-oxo corrolazines. Both of these compounds were characterized by a number of spectroscopic methods and crystals suitable for X-ray diffraction were examined in the case of the manganese(III) corrolazine. Also, the binding properties of manganese(III) corrolazine was studied and was useful in understanding properties of the manganese(III) corrolazine in later chapters.; The focus of chapter 3 is the characterization of a manganese(V)-imido corrolazine. Crystals suitable for X-ray diffraction were examined and this is the first example of a high-valent manganese corrolazine complex that has been characterized in this manner. Cyclic volammetry revealed that this complex could not easily be reduced, which was surprising due to the high oxidation state of the manganese. However, the CV revealed two reversible oxidations, one of which was examine chemically, forming a manganese(V) pi-cation radical species that was characterized by UV-vis and EPR.; Chapter 4 details the ability of the manganese(V)-oxo corrolazine to abstract a hydrogen atom from both O-H and C-H bonds. A kinetic study of hydrogen atom transfer from a series of para-substituted 2,6-di- tert-butyl phenols revealed a reaction rate enhancement with an increase in electron-donation from the para group. A kinetic isotope study revealed that hydrogen was indeed involved in the rate determining step of the reaction. Gas chromatography of reaction mixtures pointed to a mechanism that involved a highly reactive manganese(IV)-OH species that further reacted with substrate to form the more stable manganese(III) complex.; In chapter 5 it was shown that the manganese(III) corrolazine was capable of activating O-O bonds from H2O2 and alkyl hydroperoxides. A detailed axial ligand study showed that H2O2 would not react with manganese(III) corrolazine without the presence of an axial ligand. It was also found that electron-withdrawing groups increased the heterolysis of the O-O bond while electron-donating groups increased the homolysis of the O-O bond. A detailed discussion of the first anionic manganese(III) corrole crystal structure and a manganese(III)-DMF crystal structure is also included.; Chapter 6 discusses an attempt at synthesizing new electron-deficient corrolazines. While that particular goal was unsuccessful an exciting tripyrrolic compound was synthesized. The tripyrrole was fully characterized and was found to be capable of binding anions and can act as a fluoride sensor. Crystals suitable for X-ray diffraction of the tripyrrole was also synthesized.

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