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

催化剂是一种加速或促进化学反应的物质。催化剂对化工和制药行业至关重要，在这些行业中，催化剂用于减少化学过程的能源需求，并指导精确的化学转化细节。许多最活跃的催化剂都是基于昂贵的稀有金属。当前研究的一个重要领域是寻找廉价、丰富的替代品来替代现有的金属催化剂。乔治亚大学化学系Gregory H.Robinson博士在化学部化学合成计划的支持下，制造和研究含有丰富元素(包括硅和铝)的高活性化合物。这种方法使用了激进的化学方法。大多数化合物含有偶数个电子，而自由基含有奇数个。这使得自由基化合物能够稳定带有不寻常电荷的金属；具体地说，它允许硅、铝或其他丰富的元素模仿目前用于催化剂的稀有、昂贵金属的行为。从事这项工作的化学专业学生获得宝贵的技能，使他们能够进入技术先进的劳动力大军。罗宾逊教授致力于向广泛的学生介绍化学(以及一般的科学)。他的演讲包括访问陷入困境的高中，与学生谈论化学/科学领域的职业。他是来自代表不足群体的个人的独特榜样，并指导了许多后来在学术界和行业担任职位的学生。该项目利用N-杂环卡宾(NHCs)和阴离子二硫杂烯自由基来形成和稳定不寻常的主要基团物种。含有二硫杂环戊烯基团的13族元素是由二硫杂环戊烯锂自由基与XER2(X=卤化物，E=13族元素，R)反应得到的。它们与NHC结合，产生未成对的电子主要与主基原子相关联的自由基。NHCS与二硫杂环戊烯配体一起形成含有E-O键或E=O键的物种(E=主族元素，O=氧)。NHC稳定的氯硅烷和膦反应生成S杂环硅烯和膦，然后扩展到含有E-E键的物种。这些化合物用通常的化学和物理方法进行了表征。该项目允许研究卡宾-二硫杂环戊烯自由基界面上大量未被探索的低氧化态、富含稀土的化学元素的合成和结构化学。该项目还包含一个面向代表不足群体的一系列学生的外展/指导部分。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

A catalyst is a substance that speeds or otherwise facilitates a chemical reaction. Catalysts are critical to the chemical and pharmaceutical industries, where they are used to reduce energy requirements of chemical processes and to guide the details of precise chemical transformations. Many of the most active catalysts are based on expensive, rare metals. An important area of current research is to find cheap, abundant replacements for the current metal catalysts. Dr. Gregory H. Robinson, Chemistry Department, the University of Georgia, is supported by the Chemical Synthesis Program of the Chemistry Division to make and study highly reactive chemical compounds containing abundant elements including silicon and aluminum. The approach uses radical chemistry. Most chemical compounds contain an even number of electrons, while radicals contain an odd number. This gives the radical compounds the ability to stabilize metals with unusual electrical charges; Specifically, it permits silicon, aluminum, or other abundant elements to mimic the behavior of the rare, expensive metals that are currently used in catalysts. Chemistry students engaged in this work acquire valuable skills to permit them to enter the technologically sophisticated workforce. Professor Robinson is committed to presenting chemistry (and science in general) to a broad range of students. His presentations include visits to troubled high schools to talk to the students about careers in chemistry/science. He is a unique role model for individuals from underrepresented groups and has mentored a number of students who have gone on to positions in academia and industry. This project utilizes N-heterocyclic carbenes (NHCs) and anionic dithiolene radical ligands to form and stabilize unusual main group species. Group 13 element containing dithiolene radicals are obtained from the reactions of lithium dithiolene radicals with XER2 (X=halide, E = group 13 element, R). These combined with NHCs give radicals where the unpaired electron is primarily associated with the main group atom. NHCs together with the dithiolene radical ligands are used to form species containing E-O or E=O bonds (E = main group element, O = oxygen). Reactions of NHC stabilized chlorosilanes and phosphines give S-heterocyclic silylenes and phospheniums, which is then extended to species containing E-E bonds. These compounds are characterized by the usual chemical and physical methods. This project allows the study of the largely unexplored synthetic and structural chemistry of low-oxidation state, earth-abundant chemical elements at the carbene-dithiolene radical interface. The project also contains an outreach/mentoring component that targets a range of students from underrepresented groups.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.