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。催化剂对化学和制药行业至关重要，它们用于降低化学过程的能源需求，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。目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.博士罗宾逊，化学系，格鲁吉亚大学，是由化学部的化学合成计划的支持，使和研究含有丰富的元素，包括硅和铝的高活性化合物。该方法使用自由基化学。大多数化合物含有偶数个电子，而自由基含有奇数个电子。 这使得自由基化合物能够稳定具有不寻常电荷的金属;具体而言，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。 罗宾逊教授致力于向广大学生介绍化学（和一般科学）。 他的演讲包括访问陷入困境的高中，与学生谈论化学/科学职业。他是一个独特的榜样，个人从代表性不足的群体，并指导了一些学生谁已经去了在学术界和工业界的职位。该项目利用N-杂环卡宾（NHC）和阴离子二硫杂环戊烯自由基配体形成和稳定不寻常的主族物种。含第13族元素的二硫杂环戊烯自由基由锂二硫杂环戊烯自由基与XER 2（X=卤化物，E =第13族元素，R）反应获得。这些与NHC结合产生自由基，其中未成对电子主要与主族原子缔合。NHC与二硫杂环戊烯自由基配体一起用于形成含有E-O或E=O键（E =主族元素，O =氧）的物质。NHC稳定的氯硅烷和膦反应得到S-杂环亚甲硅烷基和膦，然后扩展到含有E-E键的物种。这些化合物通过通常的化学和物理方法表征。该项目允许研究在卡宾-二硫杂环戊烯自由基界面的低氧化态、地球上丰富的化学元素的基本未开发的合成和结构化学。该项目还包含一个外展/辅导部分，目标是来自代表性不足群体的一系列学生。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。

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.