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

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With funding from the Chemical Synthesis Program in the Chemistry Division, Professor Gregory H. Robinson of the University of Georgia, will study the synthetic inorganic chemistry of compounds based on inexpensive, abundant, non-metallic elements. The goal is to develop catalysts based upon readily available main group elements as alternatives to traditional industrial catalysts that are often based upon rare and expensive transition metals. The key target in this research is a class of compounds called dithiolenes that contains two sulfur atoms and can accept and/or donate electrons in chemical reactions. Since the ability to provide or accept electrons is one of the key properties of most transition metal catalysts, the use of dithiolenes to perform a number of industrially important processes will be evaluated. Students engaged in this work will acquire skills in manipulating unusual chemical compounds. In addition, they will be trained in public speaking and writing skills. The PI will continue his efforts to extend the chemistry research enterprise to women and African Americans.This project will synthesize a number of main group-based dithiolene radicals and explore their structure and reactivity. An important goal is to ascertain if main group-based dithiolene radicals can activate small, energy-rich molecules. Specifically, a set of Lewis base-stabilized dithiolene zwitterions (LO) will be prepared. These will be used to explore: (a) the activation of small molecules using LO, (b) the thermally or optically induced single electron transfer involving LO, (c) the development of LO-anchored Lewis acid/base pairs, (d) the "naked" dithiolene radical-NHSi-polysulfide three-component systems for ring opening of cyclic ethers and esters, (e) magnesium dithiolene radicals, and (f) group 13 and 14 element-based tris(dithiolene) triradicals. The proposed work will attempt to answer several fundamentally important questions, including: Are redox-active ligands capable of activating small molecules in a metal-free environment? The project will provide training and education for a diverse group of students and postdoctoral associates. In addition, the PI is an active participant in a wide range of efforts to increase the diversity of both students and faculty in science.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.