Date of Graduation

12-2025

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry (PhD)

Degree Level

Graduate

Department

Chemistry & Biochemistry

Advisor/Mentor

Kilyanek, Stefan

Committee Member

He, Maggie

Second Committee Member

Allison, Neil

Third Committee Member

Coridan, Robert

Keywords

Deoxydehydration catalysis; Molybdenum-dioxo ccomplexes; Proton-coupled electron transfer

Abstract

This dissertation details the design, development, and synthesis of a molybdenum-dioxo complex bearing a trispyrazolylborate ligand. The system was tested for its efficiency as a catalyst for deoxydehydration with a small substrate scope. Deoxydehydration reactions with 1-phenyl-1,2-ethanediol, diethytartrate, and 1,2-octanediol show low yields with catalytic turnover only found for diethyltartrate. Electrochemical studies show well behaved PCET behavior with two distinct electron transfer events in the presence of a proton donor. Studies of two molybdenum-dioxo complexes bearing dianionic pincer ligands were conducted to expand further on systems that have been extensively studied in our lab. Deoxydehydration of glycerol by a molybdenum-dioxo catalyst bearing a dianionic pincer ligand was studied. The production of allyl alcohol was successful with low yields when the catalyst was heated with neat glycerol. The impact of proton donors and acceptors was studied using a molybdenum-dioxo catalyst bearing a dipicolonate ligand. It was observed that the addition of proton donors and acceptors to DODH reactions with discrete catalysts do not enhance the reaction. Ruthenium polypyridyl complexes bearing distal basic sites were synthesized and characterized. These complexes are to be studied further within the group for ability to electrochemically activate C-H and O-H bonds.

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