Date of Award:

8-2024

Document Type:

Dissertation

Degree Name:

Doctor of Philosophy (PhD)

Department:

Chemistry and Biochemistry

Committee Chair(s)

Lisa M. Berreau

Committee

Lisa M. Berreau

Committee

Alvan C. Hengge

Committee

Kimberly J. Hageman

Committee

Gang Li

Committee

Jixun Zhan

Abstract

Almost everything we interact with on a daily basis has been synthesized by chemists ranging from plastics, food preservatives, and medications. The diversity of synthetic molecules are achieved by the formation of new bonds between existing molecules and/or through the cleaving of bonds found in a molecule. There are uncountable amount of conditions reported to facilitate chemical reactions which all depend on the nature of molecules being used and the environment it is used in.

In recent years, more attention has been paid to identify chemical reactions that can use more environmentally favorable conditions and reduce the use of limited and expensive reagents. Specifically, certain carbon-carbon (C-C) bonds require harsh conditions and expensive transition metals to facilitate C-C bond cleavage. The Berreau lab has worked on understanding how to cleave C-C bonds in a family of molecules classified as β-diketones. More readily available copper, nickel and cobalt transition metal complexes were used in conjunction with environmentally friendly diatomic oxygen (O2) to facilitate the cleavage of a specific C-C bond in the β-diketone. A portion of the work presented herein builds upon the understanding of the nature of the metal center on the reaction between O2 and β-diketones.

Another family of molecules that are of interest to the Berreau group are flavonols. Flavonols are found in plants and vegetables that are consumed by humans and have beneficial health effects associated with them. Our lab has synthesized a π-extended flavonol (Flav-1) that has found application in biomedical applications owing to its ability to release carbon monoxide (CO) under specific conditions. While toxic and high concentrations, CO is an endogenously produced signaling molecule that has health benefits at low concentrations. Numerous studies have been performed to understand neutral Flav-1’s CO release properties in solution and in biological environments. Chapter three of this dissertation discusses the solution, toxicity and CO release properties of a Cu(II)-Flav-1 complex as it compares to neutral Flav-1. The last chapter investigates the thermal solution properties and O2 reactivity leading to CO release of the anionic form of Flav-1.

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