CAREER: Using Metal-Organic Frameworks to Harness Molecular Catalysts for Selective C-H Functionalization

With funding from the Chemical Catalysis program in the Division of Chemistry, Professor Wade of The Ohio State University will address the challenges in C–H bond functionalization by investigating the design of new heterogeneous catalysts containing immobilized transition metal complexes capable of selective C–H bond activation. Catalytic C–H bond functionalization offers a powerful and efficient means of preparing complex organic molecules used in the pharmaceutical and fine chemical industries.

However, many catalysts currently employed for C–H functionalization reactions rely on rare and expensive metals and require high loadings to achieve a desirable level of activity. In addition, there is a growing need for catalysts capable of facilitating site-specific functionalization in substrate molecules containing multiple C–H bonds. This research will develop greater understanding of the effects of catalyst immobilization on catalytic activity and product selectivity, and has the potential to impact the production of fine chemicals.

Dr. Wade will integrate his research with outreach activities that promote student engagement in science, technology, engineering and mathematics (STEM) disciplines. Dr Wade and his team will be involved in Virtual Meet a Scientist and Bringing Opportunities for Research Involvement to Chemistry Classrooms (BORICC) programs that connect researchers with high school science classrooms in regions that lack access to STEM outreach opportunities.

These programs are designed improve student perceptions of scientists, increase enthusiasm for pursuing STEM-based careers, and support secondary education goals and curricula in STEM fields.

Catalyst deactivation processes such as dimerization and ligand disproportionation are prevalent in homogeneous reactions. Metal-organic frameworks (MOFs) offer versatile platforms for the design of single-site heterogeneous catalysts that are resistant to intermolecular deactivation and decomposition processes owing to site-isolation effects. The well-ordered structures of MOFs also offer unprecedented opportunities to manipulate the secondary coordination sphere around a catalytic site and enable regio- or chemo-selective transformations.

With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Wade will investigate new strategies for the design MOF-based C–H borylation and amination catalysts containing framework-immobilized, organometallic active sites. These studies exploit the well-defined spatial arrangement of linkers and metal nodes to engender non-covalent interactions that chaperone substrates for site-selective C–H bond activation.

Benchmarking studies will be employed to evaluate the effect of different catalyst immobilization strategies and MOF supports on catalytic activity and selectivity. Structure-property relationships will be developed and applied for design optimization of site-selective C–H borylation and amination catalysts.

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.