RUI: Advancing the State of the Art in Metal-Ligand-Cooperative Hydrogenation through Mechanistic Understanding

In this project, Professors Anthony Chianese and Jason Keith of Colgate University are working to improve the efficiency of industrially useful catalytic chemical reactions by understanding how they proceed at the molecular level. By working to understand exactly how the chemical bonds change as simple molecules are converted to more complex and high-value products, we can develop improved catalysts to reduce chemical waste, improve energy efficiency, and provide access to new types of useful molecules. The team is using a combination of laboratory experiments and computer modeling to provide a complete understanding of how the reactions work. Understanding how the reaction works at a microscopic level contributes to basic scientific knowledge and facilitates the design of the next generation of improved catalysts. All of the research for this project is being conducted by undergraduate students in the PIs’ laboratories at Colgate. Participation in undergraduate research, especially early in a student’s career, is increasingly recognized for its positive impacts on students and for broadening participation in the sciences. PI Chianese and the students working in his research group devote a day each summer to an outreach activity for high school students attending Camp Fiver, a residential summer camp that hosts a group of at-risk students from New York City and rural upstate New York. In this project, PIs Chianese and Keith are using a combined experimental/computational approach to study the mechanisms of transition-metal catalysts for the hydrogenolysis of esters and amides, with the aim of using the knowledge gained to advance the state of the art in these reactions. Many catalysts for ester and amide hydrogenation selectively give products where the C-O or C-N single bonds are cleaved, while few are known to selectively promote reduction of the carbonyl group to a methylene group. To date, no comprehensive mechanistic analysis has been conducted on ester or amide hydrogenation catalysts known to reduce carbonyl groups. By developing an understanding of the mechanistic origins of this selectivity pattern, we aim to develop improved catalysts ester and amide reduction, with a broader scope of applicable substrates and with reduced use of expensive Lewis acid additives. 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. NSF Award ID: 2555885 | Program: 01002627DB NSF RESEARCH & RELATED ACTIVIT | Principal Investigator: Anthony Chianese | Institution: Colgate University, HAMILTON, NY | Award Amount: $350,000 View on NSF Award Search: https://www.nsf.gov/awardsearch/show-award/?AWD_ID=2555885 View on Research.gov: https://www.research.gov/awardapi-service/v1/awards/2555885.html