RUI: Development of a Non-Cooperative Ruthenium Catalyst for Ester Hydrogenation

Colgate University, Hamilton NY

Investigators

Abstract

Many of the current methods for carrying out chemical reactions rely on the use of expensive and/or toxic reagents, and often produce large amounts of chemical waste. In this project, Professors Anthony Chianese and Jason Keith are working to develop more sustainable methods to achieve the same results by designing robust, highly active metal catalysts, in particular for hydrogenation reactions. In developing the next generation of improved catalysts for these reactions, it is essential to understand how the catalysts work at the molecular level. Therefore, an important part of this project involves combining experimental and theoretical knowledge to build a comprehensive and detailed understanding of these catalysts and their reactions. 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. PI Chianese and the students working in his research group devote a day each summer to running an outreach activity for high school students attending Camp Fiver, a residential summer camp that hosts a group of at-risk students New York City and rural upstate New York. With funding from the Chemical Catalysis Program of the Chemistry Division, Professors Anthony Chianese and Jason Keith of Colgate University are developing new catalysts for the hydrogenation of esters. Recently, highly efficient catalysts have been developed for the hydrogenation of a wide array of polar substrates, spurred by the disclosure of Milstein's PNN-pincer-ruthenium system that is active for the hydrogenation of esters to alcohols and the reverse reaction. Currently, all of the most efficient catalysts for this class of transformation are developed based on an expected metal-ligand cooperative mechanism. Chianese and Keith have recently discovered a catalyst for ester hydrogenation based on a CC-chelating ligand whose structure suggests that a non-cooperative mechanism is likely operative. The goal of the project is to develop and optimize this catalyst system through modification of the catalyst structure, while devoting significant effort to building a thorough mechanistic understanding through experiment and computation. 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. PI Chianese and the students working in his research group devote a day each summer to running an outreach activity for school students attending Camp Fiver, a residential summer camp that hosts a group of at-risk students New York City and rural upstate New York.