CAREER: CAS: Understanding the Chemistry of Palladium and Silyl Compounds to Design Catalyst Active Sites

University Of Oregon Eugene, Eugene OR

Investigators

Abstract

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Amanda Cook-Sneathen of the Department of Chemistry and Biochemistry at the University of Oregon is developing new catalysts by understanding the interactions of molecules at a liquid-solid interface. The ultimate goal of this research program is to develop solid catalysts that have an active site – the location of chemical reactions on a catalyst – that is structurally understood. Solid catalysts are used ubiquitously in the chemical industry but understanding how they function is significantly challenging. Only with knowledge of the active site structure on a molecular level can one develop hypotheses on how to improve reactions. In this project, active sites made of palladium will be installed on the surface of silica (the primary component of sand and glass) to synthesize solid catalysts, and their activities and mechanisms of action will be investigated. This research program sits at the interface of organic and inorganic chemistry and homogeneous and heterogeneous catalysis and has the potential to contribute to a more sustainable future. Students working on this project will benefit intellectually and practically because of the interdisciplinary nature of the research. Mentorship, immersion of high-school students in chemistry labs, and increasing diversity, equity, and inclusion through outreach are also parts of the project. Heterogeneous catalysis is vital in the chemical industry, where it is used in >90% of chemical processes. These catalysts are integral to sustainable practices, since they are robust and recyclable. Improvement of heterogeneous catalysts is often empirical and is hindered by a lack of structural understanding of the active site, precluding informative mechanistic studies. This project utilizes surface organometallic chemistry to control the structure and reactivity of metal sites on surfaces, specifically palladium sites supported on silica. There are three Aims: 1) Surface-supported (silyl)Pd(H) species will be formed and their reactivity as catalysts for alkene isomerization will be tested; 2) Oxidative addition of silyl halides to palladium complexes will be investigated; 3) Cationic, surface-supported palladium sites will be synthesized, and their catalytic activity in the Diels-Alder reaction will be demonstrated. In addition to the research goals, there are several complementary educational goals: 1) educate through effective mentorship, 2) increase representation in STEM, and 3) increase awareness of contributions of chemists from underrepresented and marginalized groups. 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.