Date of Award


Document Type

Campus Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

First Advisor

Jonathan Rochford

Second Advisor

Daniel Dowling

Third Advisor

Niya Sa


In recent years, the development of transition metal based electrocatalysts has made the utilization of carbon dioxide as a renewable feedstock for energy dense carbon-based fuels more realistic. The proton-coupled electrochemical reduction of CO2 provides an accessible route to the generation of fuels (CH3OH and HCO2H) and fuel precursors (CO and H2). Selective production of CO using Mn(I) and Re(I) centered polypyridyl catalysts has been well established, however, tuning the ligand scaffold to alter the product selectivity, reaction kinetics and efficiency has garnered a lot of momentum over the past few years. It was recently established that second coordination sphere effects have an influential role in the reaction route and thus product generation. The scope of this thesis is to investigate how electronic inner sphere and second coordination sphere pendant functionalities influence the class of [fac-MnX(L2)(CO)3] pre-catalysts where L2 is a bidentate redox-active or non-innocent ligand and X is a monodentate ancillary ligand. By introducing ligand functionalities that can directly participate in catalysis, the goal of these studies is to favorably impact reaction rate and overpotential, or selectively tune product generation.


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