CAS: Electrochemical Ionic Hydrogenation: Promoting Carbonyl and Imine Reduction through Electrocatalysis

With the support of the Chemical Catalysis program in the Division of Chemistry, Kate M. Waldie of Rutgers, The State University of New Jersey is studying strategies to prepare valuable chemical products using electrochemistry. The goal of this project is to develop more sustainable methods for producing chemicals using renewable, sustainable energy. The proposed research will involve experiments to understand how catalyst structure and reaction conditions combine to achieve high reaction efficiency and selectivity. This knowledge will have important applications in electrocatalyst design for sustainable chemical manufacturing. The project will also provide training for students in synthetic chemistry, catalysis, and electrochemistry. The Waldie group will continue to engage in outreach activities that promote the equity and inclusion of students from traditionally underrepresented populations, including a recurring symposium series entitled Diversity in Chemistry that highlights the careers and perspectives of chemists from diverse backgrounds. Dr. Waldie will also develop new lecture and laboratory teaching resources for electrochemistry education. This project will develop the electrochemical ionic hydrogenation of carbonyl and imine substrates using transition metal-hydride complexes in the presence of Brønsted or Lewis acid promotors. This electrocatalytic approach to hydrogenation circumvents the need for hydrogen gas or stoichiometric reductants. However, avoiding the competitive hydrogen evolution reaction (HER) is a significant challenge for electrochemical reduction reactions. The proposed research will utilize detailed electrochemical, kinetic, and mechanistic studies to examine how substrate activation with an acid can direct the reactivity of metal-hydride complexes toward electrochemical hydrogenation over HER. This project aims to establish a thermodynamic framework in which the properties of the metal-hydride electrocatalyst and acid promoter are optimized to achieve high selectivity and high faradaic efficiency for substrate reduction. The goal is to investigate a large reactivity scope and establish principles and methods to advance the electrification of carbonyl and imine hydrogenation for sustainable organic synthesis. 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.