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

催化剂是一种加速或以其他方式促进化学反应的物质。催化剂对化学和制药工业至关重要，它们被用来减少化学过程的能量需求，并指导精确化学转化的细节。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、丰富的金属催化剂替代品。Gregory H. Robinson博士，乔治亚大学化学系，在化学系化学合成项目的支持下，制造和研究含有丰富元素（包括硅和铝）的高活性化合物。这种方法使用了自由基化学。大多数化合物含有偶数电子，而自由基含有奇数电子。这使自由基化合物具有稳定带不寻常电荷的金属的能力；具体来说，它允许硅、铝或其他丰富的元素模仿稀有、昂贵金属的行为，这些金属目前用于催化剂。从事这项工作的化学学生获得了宝贵的技能，使他们能够进入技术复杂的劳动力市场。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/科学的职业生涯。他是来自弱势群体的个人的独特榜样，并指导了许多在学术界和工业界担任职务的学生。本项目利用n -杂环碳烯（NHCs）和阴离子二硫代烯自由基配体形成和稳定不寻常的主基团。含有二硫代烯自由基的13族元素是由二硫代烯锂自由基与XER2 （X=卤化物，E = 13族元素，R）反应而得。它们与NHCs结合形成自由基，其中未配对电子主要与主基团原子结合。NHCs与二硫代自由基配体一起形成含有E-O或E=O键的物质（E =主族元素，O =氧）。NHC稳定的氯硅烷和膦反应得到s -杂环硅烯和磷，然后扩展到含有E-E键的物质。这些化合物用通常的化学和物理方法进行表征。该项目允许对低氧化态、地球丰富的碳-二硫烯自由基界面化学元素的合成和结构化学进行大量未开发的研究。该项目还包含针对弱势群体的一系列学生的外展/指导部分。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.