| Description |
Transition-metal electrocatalysts have previously been shown to convert carbon dioxide to carbon monoxide, which is promising for future energy schemes. Recent efforts have focused on (N^N)Mn(CO)3X complexes due to their performance and exclusion of expensive metals (X = anionic ligand, N^N = bidentate N-donor ligand). This thesis will focus on the characterization of proposed intermediates of bpy-Mn(CO)3X (bpy = 2,2- bipyridine) mediated electrocatalytic reduction of CO2 to CO. First, I will discuss the stability of the proposed [bpy-Mn(CO)4]+ species, and how it may be pertinent to a catalytic cycle for CO2 reduction. Next, I will discuss how this complex can be used to prepare bpy-Mn(CO)3COOMe, a synthetic analogue to the catalytically pertinent bpy- Mn(CO)3COOH intermediate. Finally, with this synthetic analogue, I will explore the reactivity and thermochemistry of bpy-Mn(CO)3COOMe. This is done to probe if certain conditions will favor the protonation-first pathway of CO production; this occurs at lower overpotentials than the reduction-first pathway and hence is desired. These findings will contribute to understanding how to activate the desired protonation-first pathway of CO production in the bpy-Mn(CO)3COOH system and contribute more broadly to our understanding of electrocatalytic CO2 reduction. |
