Grant: Discovery Launch Supplement

Although fossil-fuels still represent 80% of the world's energy portfolio, their depletion, and implications in global warming demand alternative fuels. Hydrogen (H2) is such an alternative that can meet growing global energy demands. Developed as early as in the 1840s, Hydrogen Fuel Cells (HFCs) convert H2 to energy and water with zero carbon emissions, contrasting against conventional modes of energy production. HFCs operate using pressurized H2 gas - an unsafe and technically challenging requirement that severely limits mobile applications. Attested by the US Department of Energy, Liquid Organic Hydrogen Carriers (LOHCs) are a promising class of candidates, albeit underutilized since high-throughput catalysis for production and storage of H2 using LOHCs still need to be developed. This research program seeks to leverage the potential of LOHCs by developing robust homogeneous catalysts that can both produce and store H2 via reversible dehydrogenation and rehydrogenation cycles. This proposal will develop a family of catalysts that feature (a) cooperative ligands that can assist in critical H-H bond cleavage/formation steps in synergy with (b) group 9 metal centers (IrIII, RhIII and CoIII) supported by a series of (c) anionic tripodal spectator ligands. These rationally designed cationic catalysts will be compatible with LOHCs while imparting the robustness needed to deter catalyst degradation under pressurized H2 in the rehydrogenation cycles. As long-term goals, we anticipate that our work will lead to successful catalysis while in the short-term, our design strategies and mechanistic investigations are expected to furnish critical insight and structure-activity-relationships (SARs) that can be translated to complimentary areas of organometallic chemistry. Students supported by this NSERC grant will gain expertise in modern organometallic synthesis, mechanistic investigations, and computational chemistry. HQP with these skills are in high demand not only in academia but also in chemical and pharmaceutical industry, as well as within the energy sector.