Sigma-Aromaticity Enabled Heavy Main Group Redox Catalysis

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor David Powers of Texas A&M University is studying new metal-free catalyst platforms for fine chemical synthesis. The use of metal-based catalysts in fine-chemical settings, such as pharmaceutical synthesis, is often expensive and imposes laborious purification processes to remove metal contaminants. The project will advance our understanding of the fundamental design elements that enable main group elements, such as iodine, to engage in efficient bond-forming processes. These insights will be used to design metal-free catalysts for an array of chemical transformations important in the preparation of functional organic small molecules. The results of the project will broadly impact the rational design and deployment of metal-free catalysts. Further, as the project investigates chemistry at the border or organic, inorganic, and main group chemistry, the project will provide training and educational opportunities to students at all education levels. With the support of the Chemical Catalysis program in the Division of Chemistry, Professor David Powers of Texas A&M University is studying iodanyl radical catalysis as a platform for metal-free oxidation catalysis that is complementary to the chemistry of diamagnetic hypervalent iodine compounds. This project will define the elementary chemical steps that are available to iodanyl radical intermediates and utilize those mechanistic insights to rationally target new catalysts and catalytic transformations. The project will advance novel catalyst design concepts based on sigma-delocalization and sigma-aromaticity of heavy main-group elements to facilitate catalyst re-oxidation and to control catalyst activity and selectivity. The project will broadly impact the design and application of metal-free catalysts and catalysis with heavy main group compounds. Because the project investigates catalyst concepts at the interface of organic, inorganic, and main group chemistry, valuable educational and outreach opportunities will impact students from all levels of scientific training. 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.