Development, Refinement, and Application of Electrochemical Methods for Evaluating Fuel-Forming Catalysts

The growing impact of climate change has fueled decades of research into renewable energy-based alternatives to fossil fuels. Homogeneous, molecular transition metal complexes have potential widespread application as fuel-forming catalysts as well as charge carriers in electrochemical energy storage technologies. One particularly appealing aspect of these complexes is their tunable ligand architecture which, when coupled with rigorous mechanistic analysis, can afford a high degree of control over molecular properties. Unfortunately, the electrochemical data that is the bedrock of this rigorous mechanistic analysis is often complicated by extrinsic factors or side reactivity. While recent advances in electroanalytical strategies have left us well-poised to evaluate catalytic mechanisms and kinetics, the question of how these tools can be exploited to identify side reactivity has been rendered comparatively out of vogue leaving it difficult to deconvolute and develop strategies to avoid these side pathways. This work has sought to improve the toolbox available for molecular electrochemists working with homogeneous transition metal complexes. One aspect of this research focuses on critically evaluating side reactivities which can greatly complicate electrochemical analysis of seemingly well-behaved systems. This work documents the challenges of reversible in situ solubility changes under electroanalytical conditions, where a change in redox state or the addition of substrate instigates the aggregation and precipitation of the transition metal complex while maintaining the integrity of the molecular core. A second aspect has been exploring new strategies for studying multi-electron fuel-forming transformations using rotating disc electrochemistry. As a whole, this research has been built on a single fundamental premise: that electrochemical analysis of transition metal complexes is often confusing and scary, but never insurmountable.Doctor of Philosoph