Inspiration, Frustration, and Fascination: An Excursion into Low-Oxidation State Main Group Chemistry

Dr. Gregory H. Robinson and Dr. Yuzhong Wang of the University of Georgia will work on a project that addresses an important aspect of advanced industrial chemical manufacturing. Most industrially important molecules are traditionally based on rare and expensive transition metals (such as gold, silver, platinum, palladium). Robinson and Wang will study the possibility of replacing these transition metal species with molecules based on more affordable, less toxic, and earth-abundant elements (such as carbon, nitrogen, sulfur, and silicon). Some of these earth-abundant metal-free substances have already shown promise in the activation of important molecules such as ammonia and water. Another goal of this project is to develop a synthetic strategy to prepare soluble silicon oxide molecular clusters. Silicon oxide clusters play a key role in our understanding of the dynamics of silicon-etching processes in the semiconductor industry—including chip production for Artificial Intelligence (AI). Students engaged in this research will be well-suited to competitively participate in the ever-expanding global chemistry enterprise. In addition, significant effort will be directed toward increasing scientific literacy. Dr. Robinson will present a series of science lectures to primary and secondary students at local schools, and he will also present lectures to residents of retirement communities. The goal is to tout both the virtue and power of science. Redox-active ligand-based transition metal complexes have shown remarkable efficacy in the activation of important small molecules (such as H2O, NH3, and H2). The pursuit of transition-metal-like behavior from main group elements has emerged as an intriguing research focus for chemists. While dithiolenes represent a well-established class of redox-active non-innocent ligands in transition metal chemistry, the coordination chemistry of main group elements with these ligands has only lately begun to be extensively investigated. The Robinson-Wang laboratory will develop the intriguing chemistry at the dithiolene-main group element interface in three main areas: (1) Dithiolene- and Lewis Base-scaffolded unsaturated silicon clusters and their silicon oxide derivatives; (2) Dithiolene radicals and their utility in the synthesis of carbide/silicide-iron-sulfur clusters; and (3) carbene-stabilized dithiolene (L0) zwitterions acting as synergic bifunctional molecular systems in small molecule activation. The project has the potential to advance fundamental main group chemistry and further the understanding of electronic structure and spin-spin interactions in radical and diradical compounds. 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.