Mechanisms in non-heme iron oxidation catalysis: Photochemistry and hydrogen peroxide activation

In this thesis, we focus mainly on the photo activation non-heme iron complexes, as well as mechanisms of thermal reactions of non-heme iron complex with H2O2.
Chapter 2, 3 and 4, focus on photochemically induced activation of iron complexes in the Fe(IV) and Fe(III) oxidation states.In chapter 2, the direct activation of non-heme iron(IV)-oxo complexes and the mechanisms involved are explored. In chapter 3 the photo-catalytic oxidation of methanol under aerobic
conditions reveals the involvement of a photo-active non-heme miu-oxo bridged diiron(III) complex and its mechanism for photo-induced
disproportionation. In chapter 4, the photo-induced oxidative degradation of the non-heme iron polypyridyl complexes under basic conditions are explored
and the implications the conclusions reached hold in regard to ligand design is discussed. Chapters 5 and 6 focus on the mechanism of thermal generation
of high-valent iron(IV)-oxo complexes by reaction of non-heme iron(II) complexes with H2O2. In chapter 5, the generation of an iron(IV)-oxo complex via heterolysis of an O-O bond in an Fe(III)-OOH species formed with stoichiometric H2O2 is focused on. In chapter 6, a novel reaction pathway for the reaction of iron(III)-hydroperoxo species with H2O2 is established. This pathway is kinetically favored compared to the homolytic cleavage of the O-O bond in
Fe(III)OOH, which would form high-valent iron(IV)-oxo species. The reaction pathways described are shown to be detrimental to the efficiency of the
complexes in the catalytic oxidation of organic substrates.