Spectroscopic and Structural Characterization of Reactive Metal Nitrenoids
Date
2022-05-19Metadata
Show full item recordAbstract
C–H bonds are the most ubiquitous functional groups found in nature. While C–H bonds are abundant, they are oxidatively robust due to the lack of polarity about the C–H bond and resulting high bond dissociation energy. Classic methods to functionalize unactivated C–H bonds are based on free-radical processes, which typically proceed with preference for cleavage of the weakest available C–H bond but are not highly selective. Significant research effort has been pursued towards selective C–H functionalization using transition metal complexes. Terminal metal–ligand (M–L) multiply bonded species (L = CR³⁻, CR₂²⁻, O²⁻, NR²⁻, and N³⁻) are now known to be ubiquitous intermediates in both biological. and metal-catalyzed synthetic C–H functionalization reactions.
This dissertation will present efforts to develop new platforms to characterize reactive terminal M–L multiply bonded species. The first three chapters discuss the relevant literature and associated challenges with designing appropriate photoprecursors to access M–L multiply bound species on Mn and Cu centers. We also discuss photoreduction, where the apical M–L bond is cleaved instead of generating a reactive intermediate, and how designing photolabile groups such as N–I moieties help bias L–X cleavage over M–L 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 M–L 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.
Subject
Reactive IntermediateNitrene
Metal Nitrene
Photochemistry
Crystallography
Photocrystallography
Citation
Van Trieste III, Gerard Pierre (2022). Spectroscopic and Structural Characterization of Reactive Metal Nitrenoids. Doctoral dissertation, Texas A&M University. Available electronically from https : / /hdl .handle .net /1969 .1 /197738.