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

在化学系化学合成项目的资助下，格雷戈里·H·格鲁吉亚大学的罗宾逊将研究以廉价、丰富的非金属元素为基础的化合物的合成无机化学。目标是开发基于容易获得的主族元素的催化剂，作为通常基于稀有和昂贵的过渡金属的传统工业催化剂的替代品。这项研究的关键目标是一类被称为二硫烯的化合物，它含有两个硫原子，可以在化学反应中接受和/或提供电子。由于提供或接受电子的能力是大多数过渡金属催化剂的关键性能之一，因此将评估使用二硫代烯烃进行许多工业上重要的过程。从事这项工作的学生将获得操纵不寻常的化合物的技能。此外，他们还将接受公开演讲和写作技能的培训。PI将继续努力将化学研究事业扩展到女性和非洲裔美国人。该项目将合成一些基于主基的二硫纶自由基，并探索其结构和反应性。一个重要的目标是确定基于主基的二硫杂环戊烯自由基是否可以激活小的、能量丰富的分子。具体而言，将制备一组刘易斯碱稳定的二硫杂环戊烯两性离子（LO）。这些将用于探索：（a）使用LO活化小分子，（B）涉及LO的热或光诱导的单电子转移，（c）LO锚定的刘易斯酸/碱对的发展，（d）用于环醚和酯开环的“裸”二硫杂环戊烯自由基-NHSi-多硫化物三组分体系，（e）二硫杂环戊烯镁自由基，和（f）基于第13和14族元素的三（二硫杂环戊烯）三自由基。拟议的工作将试图回答几个根本性的重要问题，包括：氧化还原活性配体能够在无金属环境中激活小分子吗？该项目将为不同群体的学生和博士后提供培训和教育。此外，PI还积极参与各种努力，以增加学生和教师在科学方面的多样性。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。

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.