Cation-Controlled Catalysis with Pincer-Crown Ether Complexes

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With the support of the Chemical Catalysis Program in the Division of Chemistry, Alexander Miller of the University of North Carolina-Chapel Hill will study the ability of simple ions to control the outcomes of catalytic organic transformations. Well-defined catalysts will be prepared and tested for their ability to alter their structure and function upon addition of ions. In addition, the project will provide a platform for training a diverse group of students in chemical synthesis, thermodynamic and kinetic mechanistic analysis, and catalyst development. Such cation-controlled catalysis will likely provide access to specific alkene isomers that are valuable in the fragrance, pharmaceutical, and commodity chemical industries, but are currently difficult to obtain. The project will impact the broader chemistry community through a web-based resource, namely the “Safety Net”, that assembles standard operating procedures from chemistry research laboratories for broad dissemination to improve the culture of safety. In this research, Dr. Alexander Miller and his research team at the University of North Carolina-Chapel Hill will study how cation–macrocycle interactions can be harnessed to control the selectivity of catalytic transformations involving alkenes. Macrocycle-containing “pincer-crown ether” ligands will provide versatile platforms, when appended to catalytically active metal centers, for understanding how non-covalent interactions influence catalyst structure and reactivity. A particular focus will be on the development of strategies to control catalyst selectivity based on either substrate–catalyst or ion–catalyst interactions. The approach to these studies is to pair catalysis studies with detailed thermodynamic and kinetic mechanistic examinations to elucidate the design principles of ion-controlled catalysis. These adaptable “responsive catalysts” will allow for the exploration of new concepts in non-covalently controlled catalysis. The research will provide foundational knowledge for improved catalyst design and development.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.