Switchable Catalysis with Cation-Responsive Ligands

University Of North Carolina At Chapel Hill, Chapel Hill NC

Investigators

Abstract

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Alexander Miller of the University of North Carolina at Chapel Hill is studying the ability of ions to control the outcomes of catalytic organic transformations of alkenes and alkynes. The research is inspired by Nature’s enzyme catalysts, which can respond to stimuli to change their structure and function. Synthetic cation-responsive catalysts will be prepared, enabling applications in switchable and tunable catalysis that could lead to more efficient and safer methods for preparing organic compounds. The project provides a platform for training graduate students in inorganic synthesis, thermodynamic and kinetic mechanistic analysis, and catalyst design and development. The project will impact the broader chemistry community through The Safety Net, a web resource designed to enhance communication about laboratory safety with synthetic chemists across the world. With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Alexander Miller of the University of North Carolina at Chapel Hill is studying how organometallic catalysts with supramolecular receptor sites can enable cation-responsive transformations of alkenes. This project focuses on compact organometallic catalysts with cation receptor sites, particularly crown ethers, that can respond to external stimuli to alter the activity or selectivity of a reaction. The research approach involves synthesizing catalysts with structurally responsive cation receptor sites, developing catalytic reactions with switchable activity and selectivity that can be combined for tandem switchable catalysis, and performing mechanistic studies to elucidate the factors influencing cation-responsive catalysis. “Pincer-crown ether” ligands have been particularly successful in enabling cation-controlled catalysis, driving planned development of methods for tandem switchable catalysis. The broader research impacts of responsive catalysts include more sustainable synthetic schemes that combine several steps to minimize solvent use and separations, and access to molecules or materials that would be difficult to access with other methods and could be valuable in the fragrance, pharmaceutical, and commodity chemical industries. 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.