Organometallic and Coordination Chemistry Approaches to Small Molecule Activation Relevant to Renewable Energy and Resources

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This program focuses on molecular approaches to deriving organic fuels and chemicals from carbon dioxide through exploring its organometallic chemistry. While infamous for both its stability and its role as a greenhouse gas, carbon dioxide is also cheap, abundant, non-toxic and renewable. Developing efficient methods to convert this plentiful source of carbon into useful materials could form the basis of a new, sustainable chemical industry and energy economy that would rival a petrochemical one based on non-renewable fossil sources. The goal of my program is to design complexes that can catalyze transformations of carbon dioxide by providing lower energy pathways to its functionalization. To reduce the cost of implementation, the proposed systems are based on abundant metals and use molecular scaffolds, or ligands, to get these inexpensive metals to mimic the reactivity of their more precious counterparts. These systems draw inspiration from the molecular machinery nature uses to perform similarly challenging transformations by enabling multiple parts of a catalyst to cooperate in reacting with a substrate. In one context, ligands that can bind two metal ions of very different character will be built to test the influence of the second metal on the electronic and chemical properties of the first one. Systematic studies of this sort of cooperation are key for the development of novel catalysts targeted to carry out transformations of carbon dioxide that involve electron transfer. In a second vein, ligands that can facilitate the catalysis of coupling reactions of carbon dioxide and other small molecules using inexpensive transition metal centres will be pursued to incorporate carbon dioxide into widely used commodity chemicals. As these types of catalytic transformations are challenging for inexpensive metals, fundamental insight into exploiting the active participation of ligand scaffolds will expand the possible scenarios for precious-metal-type reactivity using abundant materials. In addition to developing the synthetic chemistry required to build our target systems, this research also aims to better our understanding of the novel reaction mechanisms involved in their use. These fundamental studies will lead to more active and selective generations of catalysts, and spread their deployment to other chemical applications. The research proposed in this program therefore holds promise of both significant environmental and industrial impact, while adding innovative new reaction pathways to the chemist's toolbox. Students participating in this research program will emerge uniquely skilled and equipped with an industrially relevant knowledge base and a sense of creativity that should be highly desirable to Canada's rapidly growing green energy and renewable resource sectors.