| Chapter 1 overviews certain aspects of the biological inorganic chemistry of nitrogen monoxide, as well as the biomimetic chemistries relevant to both its oxidation and reduction, with an emphasis on innovative current research from highly regarded research groups including our own. The bioinspired inorganic chemistry of nitric oxide is extensive and a very 'hot' subject right now, and has inspired most of the chemistry presented in this dissertation.;In Chapter 2 we present the chemistry of the synthetic heme (F8 )FeII able to effect nitric oxide dioxygenase chemistry facilitating the reaction of O2 and •NO to yield the nitrate anion NO3-; we also present its ability to effect phenol substrate nitration. The implications from the latter chemistry involve the suggestion of a highly reactive transient iron-peroxynitrite intermediate. The chemistry of metal-peroxynitrite formation and its ability to carry out further chemistry is not well understood, but in Chapter 3 we aim to significantly contribute to this field. The heme-superoxo (F8)FeIII--(O 2•-) effectively dioxygenates •NO, as described in Chapter 2, and in Chapter 3 we investigate the ability of the proposed iron-peroxynitrite intermediate to carry out nitration on a number of substrates and the implications those results have on the nature of a reactive intermediate and the mechanism by which either nitration or isomerization occurs.;The reductive coupling of •NO is discussed in Chapter 4, highlighting two synthetic heme/Cu systems that are able to effect this chemistry. The synthesis and characterization of the heme-dinitrosyl complexes 6LFe II--(NO)2 and (F8)FeII--(NO) 2 is presented, and perhaps more importantly, their use in controlling the stoichiometry of the reductive coupling of •NO relevant to NORs and HCOs is highlighted. |
