CAREER: Organic Transformations Enabled by Redox-Active Ligands and d0 Metals

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With funding from the Chemical Catalysis program in the Division of Chemistry, Dr. Courtney Roberts and her group will work toward developing a an alkyl–alkyl cross-coupling reaction that uses earth abundant and previously unutilized metals in groups 3 and 4 as catalysts for this transformation. These metals provide ideal reactivity but have not been used before for this reaction due to their electronic nature. The Roberts group is leveraging the power of catalyst design to overcome this limitation. By overcoming this challenge, other new types of reactivity beyond cross-coupling will be explored. Dr. Roberts and her group will actively engage in efforts to promote equity in both graduate and undergraduate education. These activities include a program called cheMNext that engages in educating minoritized students in chemistry about applying to graduate school as well as the development of active learning programs for undergraduate organic chemistry at the University of Minnesota.Developing new catalytic methods to form carbon-carbon bonds has the potential to impact many levels of society from agricultural chemistry to materials chemistry. Dr. Courtney Roberts and her group from the University of Minnesota are developing new reactions that require redox events using early transition metals and redox active ligands. This fresh perspective offers a new approach to address the long-standing challenges associated with alkyl–alkyl cross-coupling. The Roberts group has found that by pairing early transition metals catalysts with redox active ligands they are able to facilitate such cross-couplings even with substrates that bear beta-hydrogens. These early transition metals have not been utilized for cross-coupling previously due to their lack of d electrons and hence the inaccessibility of typical oxidative addition pathways. Their propensity to exist in the highest oxidation state, also makes reductive elimination unfavorable. By using tridentate redox-active ligands, redox chemistry can be leveraged to enable radical catalysis. Mechanistic insights will be leveraged for new multicomponent reaction development based on radical-polar crossover reactivity.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.