CAREER: Formation and Redox Chemistry of Metal Polysulfanido Complexes for Sulfur Transfer Reactions

In this CAREER project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Emily Tsui of the Department of Chemistry and Biochemistry at the University of Notre Dame is studying a new class of transition metal sulfur complexes. The goal of this research is to use these complexes for the development of new catalytic reactions and as new ways to store energy or electricity.

This project will support the training of graduate and undergraduate students to prepare them to become successful members of the scientific workforce. Additional educational outreach materials are to be developed to improve the scientific engagement of middle school students and their parents and teachers, particularly in the area of renewable energy.

Professor Tsui and her group are studying the formation of metal polysulfanido complexes via the insertion of elemental sulfur into first-row transition metal thiolate compounds. Synthetic, spectroscopic, and electrochemical studies will be carried out on these complexes to probe the relationship between polysulfanido formation and ligand ring strain or substitution.

Insights gleaned from these studies are then to be used in the design of new catalysts for sulfur transfer reactions to unsaturated organic substrates. Additionally, the Tsui team aims to develop new ways of controlling the speciation of polysulfide ions upon sulfur reduction. There are three specific aims of the research to be undertaken: (1) Elemental sulfur is to be activated by metal thiolate chelate and nonchelated complexes; (2) The Tsui research team aims to develop catalytic carbon-sulfur bond-forming reactions mediated by metal polysulfanido complexes and (3) The Notre Dame team plans to study the redox properties of metal polysulfanido complexes.

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.