Mechanistic studies aimed at understanding the interactions of various nitrogen oxides with iron, copper, and chromium model complexes

Since its discovery as an important bioregulatory molecule, there has been a large interest in understanding the reactions of nitric oxide (NO). Once formed, NO typically reacts with metal centered complexes, reinforcing the need to understand the basic mechanisms of these interactions. Another pathway for reaction involves the autoxidation of NO to NO2 in aprotic medium. Under laboratory conditions it is typically present as an impurity in the NO gas stream, and its reactivity (as well as those of the other NxOy species that subsequently form) must be distinguished from those reactions that are attributed to NO itself. Under in-vivo conditions NO2 may be formed in the hydrophobic regions of the cell, stressing the need to develop a model complex that can deliver NO2 on demand to better study its reactivity.; Discussed in this dissertation are mechanistic studies that were aimed at understanding the reactions of NO and NxOy with various iron porphyrinate complexes using quantitative rapid mixing and laser flash photolysis techniques. Studies that probed the one electron reduction of two different copper(II) model complexes by NO (termed "reductive nitrosylation") will also be discussed. From these observations and measurements, it is proposed that the two different copper complexes follow unique pathways for reaction.; In order to better understand the reactions of NO2, the synthesis of novel chromium(III) porphyrin complexes that were axially ligated by nitrate are described. In addition to their characterization, quantitative studies were aimed at investigating whether these model systems could be utilized as an effective photochemically activated, NO2 donor.