Biomimetic and organometallic oxidation catalysts related to water splitting, epoxidation and green chemistry

Metal oxo-species (M=0) are intermediates in a plethora of biological and synthetic reactions. Four types of reactivity have been explored in detail this dissertation: water oxidation (O-O bond formation), epoxidation, hydroxylation (C-O bond formation), and desaturation (C=C bond formation) are all shown to occur using Ir catalysts and biologically inspired Mn, Fe and Ir catalysts. As an introduction to this broad range of topics, the mechanisms for these processes are explored in Chapter I. Chapter 2 examines Cp* Ir catalysts in the context of water oxidation, and photocatalytic water decomposition to produce O2 and H2. In Chapters 3 and 4, Manganese porphyrins bearing molecular recognition units are explored in catalytic asymmetric epoxidation reactions. The first model reactions of desaturase chemistry are reported in Chapter 5. Finally, Chapter 6 shows Ru catalysts that are useful for the synthesis of amides by a Green Chemistry route.