Thesis
Investigation and manipulation of proton, hydride, and hydrogen atom transfer with main group compounds
Washington State University
Master of Science (MS), Washington State University
2017
Handle:
https://hdl.handle.net/2376/102715
Abstract
Catalysis provides a means towards developing greener synthetic processes, but many catalysts feature late transition metals (e.g. rhodium, platinum), which are in low abundance and can be toxic. First row transition metals and main group complexes provide sustainable routes to catalysis, but both suffer from a preference for one-electron chemistry or a lack of redox chemistry. The lack of redox chemistry limits the scope of chemical reactions that first row transition metals and main group complexes are capable of catalyzing. In order to make first row metals and main group complexes behave more like late transition metals, resulting in greener processes, redox-active ligands that act as electron reservoirs can be employed. To determine the desired characteristics for a redox-active ligand, computational thermodynamic analyses can be utilized. Herein, the computational thermodynamics for the oxidation of substituted borohydrides are used to compare the reactivity of borohydrides with metal hydrides and are shown to exhibit similar reactivity. Computational analyses also revealed that coordination of a substrate molecule to a strong Lewis acid resulted in a more favorable reduction of the substrate molecule than when coordination to a weak Lewis acid. With the understanding garnered from the computational studies, a fluorescent dye molecule, BODIPY, is integrated into a Lewis acid and a Lewis base molecule to manipulate their reactivity in chemical transformations. The redox nature of the BODIPY molecule allows for the generation of a Lewis base that is capable of catalytic proton reduction to produce dihydrogen in the absence of a metal and of fluorescent Lewis acids and bases that are capable of sensing small molecules.
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Details
- Title
- Investigation and manipulation of proton, hydride, and hydrogen atom transfer with main group compounds
- Creators
- Ian Anderson Kieffer
- Contributors
- Zachariah M. Heiden (Degree Supervisor)
- Awarding Institution
- Washington State University
- Academic Unit
- Chemistry, Department of
- Theses and Dissertations
- Master of Science (MS), Washington State University
- Publisher
- Washington State University; [Pullman, Washington] :
- Identifiers
- 99900524878201842
- Language
- English
- Resource Type
- Thesis