Synthetic, Mechanistic, and Catalytic Studies of Electrophilic d- and f-Element Complexes

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With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Tobin J. Marks of Northwestern University in Evanston, Illinois. Professor Marks and his coworkers are discovering, understanding, and optimizing new catalytic reactions, and closely combining this effort with educational outreach activities. Such catalytic processes are of great importance to the U.S. chemical industry, and it is estimated that catalysis underpins 25% of the U.S. GDP, producing fertilizers, fuels, plastics, pharmaceuticals, coatings, and other chemicals on a huge scale. Future catalytic transformations must be more efficient, non-toxic, non-polluting, and use low-cost, earth-abundant metals in more selective, sustainable, and economically competitive technologies. Addressing these challenges will require a skilled National technical workforce, and US universities are playing a major role by broadly educating young scientists to attack global-scale problems, while conducting excellent research across broad disciplinary fronts. Projects funded by this award involve a multi-faceted, educationally rigorous mix of catalyst creation, catalytic reactions, and understanding reaction products. This, combined with a highly interactive research group environment, provides excellent training/mentoring for graduate, undergraduate, and postdoctoral scholars planning industrial, national laboratory, or academic careers, and includes women and underrepresented minorities. This research is built around two integrated exploratory, hypothesis-driven themes stimulated by the unique properties of earth-abundant lanthanide (4f), actinide (5f), and d0 early transition metal complexes. In the first, catalytic reactions that create or cleave carbon-heteroelement bonds via non-traditional pathways are being developed. Unusual catalysts are being used to selectively create heteroatom (boron, nitrogen, oxygen, sulfur, phosphorus) bonds to important chemical building blocks such as olefins, alkynes, ketones, aldehydes, esters and amides, either in single or in closely coupled multiple steps. Useful substances with diverse ring structures such as pharmaceuticals and fine chemicals and being produced by this work. Topics being studied include chiral ligands for pharma-related enantioselective catalytic processes, and catalytic systems capable of reversing the aforementioned bond-forming processes to deconstruct bio-based feedstocks and other heteroatom-containing molecules. In the second theme, catalyst nuclearity effects applied to unusual olefin polymerization and hydroelementation processes are being studied. The team is using designed catalytic centers to effect polymerization reactions which link unsaturated building blocks, including those with normally deactivating polar and basic groups, to produce plastic materials with superior bulk properties including mechanical or processing properties, and/or surface properties such as adhesion, wettability, water-repellence, compatibility with other polymers, or bacteriocidal characteristics. Catalyst design includes ways to orchestrate cooperative enzyme-like processes that are "switched on" when two catalytic centers are placed in close but variable proximity with the objective of achieving unique polymerization processes. These include polymerization reactions to produce novel types of polymer architectures derived from catalysts in which two cooperating metal centers have similar or different, complementary reactivities. A second goal with such catalysts is bond-forming processes which create expanded structures accessible only by the cooperative interaction of two catalytic metal centers.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.