Synthesis, characterization, and reactivity of contracted macrocycles: Studies on triazatetrabenzcorroles and metallocorrolazines

Chapter 1 discusses recent efforts in the area of contracted macrocycles, including corroles, corrolazines, and triazatetrabenzcorroles. These compounds display a unique ability to stabilize metals in unusually high-oxidation states. This ability confers several advantages over the analogous, non-contracted macrocycles. For example, several biologically important reactions are described which involve transient, high-valent metal species which are difficult to characterize due to their unstable nature. Contracted macrocycles offer the opportunity to stabilize these states so that a better understanding of the role these high-valent intermediates play in biological processes may be gained.; Chapter 2 describes the synthesis and spectroscopic characterization of several new, highly soluble, and sterically strained, triazatetrabenzcorroles. These molecules, formed via a ring contraction reaction from parent phthalocyanine moieties, contain a central phosphorus atom in the +5 oxidation state which is inserted concomitant to the extrusion of a meso-nitrogen atom during the formation of the TBC ring. The electronic, spectroscopic, and physical characteristics of all of the synthesized compounds are discussed and the unique properties of TBC complexes are discussed relative to other contracted macrocycles.; Chapter 3 is concerned with the synthesis and characterization of vanadium and copper corrolazines. Included in this chapter is the complete electrochemical characterization of these metallo-corrolazines as well as a description of a unique acid-base behavior demonstrated in the case of the vanadium complex.; Chapter 4 discusses the preparation of iron corrolazine and the subsequent reduction of this complex to its lower oxidation state forms. Both the iron(II), and iron(I) reduced forms of the iron corrolazine are described. Following characterization, the reactivity of the iron(I) corrolazine complex with organohalides is discussed, including the efficient, and complete, stoichiometric destruction of DDT via treatment with the reduced iron complex.; Finally, Chapter 5 is a conglomeration of studies on the preparation and characterization of high-valent iron corrolazine complexes. Reaction of the iron corrolazine with several oxygen atom transfer reagents is described. The efficient oxidation of thioanisole by the oxygen atom transfer reagent CDMANO, catalyzed by iron corrolazine, is described as well as the epoxidation of cis-stilbene under the same conditions.