| Abstract: | C⁰́₃H bonds are the most ubiquitous functional groups found in nature. While C⁰́₃H bonds are abundant, they are oxidatively robust due to the lack of polarity about the C⁰́₃H bond and resulting high bond dissociation energy. Classic methods to functionalize unactivated C⁰́₃H bonds are based on free-radical processes, which typically proceed with preference for cleavage of the weakest available C⁰́₃H bond but are not highly selective. Significant research effort has been pursued towards selective C⁰́₃H functionalization using transition metal complexes. Terminal metal⁰́₃ligand (M⁰́₃L) multiply bonded species (L = CR℗đ¹́», CR²́²℗ø¹́», O℗ø¹́», NR℗ø¹́», and N℗đ¹́») are now known to be ubiquitous intermediates in both biological. and metal-catalyzed synthetic C⁰́₃H functionalization reactions. This dissertation will present efforts to develop new platforms to characterize reactive terminal M⁰́₃L multiply bonded species. The first three chapters discuss the relevant literature and associated challenges with designing appropriate photoprecursors to access M⁰́₃L multiply bound species on Mn and Cu centers. We also discuss photoreduction, where the apical M⁰́₃L bond is cleaved instead of generating a reactive intermediate, and how designing photolabile groups such as N⁰́₃I moieties help bias L⁰́₃X cleavage over M⁰́₃L cleavage. The fourth chapter discusses the chemical non-innocence of supporting ligands, and how this affects the identity of the active catalyst. The last two chapters discuss methods to structurally characterize M⁰́₃L multiply bound reactive intermediates. We demonstrate the affect changing anions bound in the primary coordination sphere has on the selectivity of the intermediate produced and discuss the design of new photoprecursors to access novel reactive structures. The electronic version of this dissertation is accessible from https://hdl.handle.net/1969.1/197738 |
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