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

化学部的化学合成计划支持乔治亚大学化学系教员格雷戈里·H·罗宾逊教授的研究项目。罗宾逊教授和他的研究团队正在研究低氧化态主族化合物的独特化学。这项研究的目的是利用有机碱(一类被称为卡宾的化合物)对高活性主基分子的独特稳定作用。例如，像硅(Si2)这样的重要分子只有在极低的温度下才能被检测到。相比之下，二磷(P2)通常只有在非常高的温度下才能检测到。罗宾逊团队已经开发出一种在室温下稳定Si2和P2(以及许多其他分子)等分子的方法，从而可以方便地研究这些重要分子的结构和反应性。特别是，这些研究人员最近报道了第一批稳定的硅氧化物分子样本。这个项目研究更雄心勃勃的硅氧化物的合成。这种化学有可能让我们更多地了解硅-氧界面，这可能会对计算机芯片和半导体产生影响。这些研究人员还将尝试合成包含大的硅和砷簇合物的分子。该项目位于主族化学的核心，这是一个传统上在欧洲受到更多重视的无机化学领域。涉及妇女和传统上代表性不足的群体的外联活动是这项研究的核心。从事这项工作的学生正在获得宝贵的合成和实验技能，这些技能使他们在就业市场上具有很高的价值。一项雄心勃勃的计划正在进行，以探索具有挑战性的低氧化主族化学领域。罗宾逊实验室已经开发出N-杂环卡宾(NHC或L：)和N-杂环二卡宾(NHDC)的衍生物，这些衍生物被用作一个独特的平台，在这个平台上可以合成稳定许多不寻常的低氧化态主要基团物种。这项工作的主要合成目标包括：(A)基于卡宾的多硅烯；(B)卡宾稳定的硅原子和簇；(C)卡宾稳定的异核双原子分子[即碳化硅，双原子III-V(13-15)物种，磷化砷(ASP)]。本实验室最近报告了难以捉摸的硅氧化物的卡宾稳定作用(自然化学)。2015，7,509)鼓励这些工作人员开发人们长期寻求的SOx分子化学。因此，合成了一系列卡宾稳定的硅氧化物(如SiO、SiO_2、SiO_2O、SiO_2O_2和SiO_3O_6等)。而硅氢化物[Si3H2和Si2H2(母体二硅炔)]正在被研究。这些卡宾稳定的氧化硅可以进一步用于开发相应的过渡金属修饰的衍生物，并将氧化硅簇合物转移到有机或有机金属底物中。此外，我们还探索了卡宾稳定的双硅烯作为二硅炔单元潜在的转移剂。研究了卡宾稳定的零氧化态主族物种的过渡金属化学。罗宾逊实验室的研究结果一再挑战无机化学中的传统结构和成键理论，其中一些已经开始出现在化学教科书中。从事这项工作的学生正在获得宝贵的合成、结晶学和计算技能。罗宾逊实验室在将化学事业扩展到更大的人力资源部门方面有着积极的记录，因为许多女性和非裔美国人都在他的实验室接受了培训。此外，罗宾逊教授还开设了一门颇受欢迎的研讨会课程，名为《改变历史的分子》。

The Chemical Synthesis Program of the Chemistry Division supports the research project by Professor Gregory H. Robinson, a faculty member in the Department of Chemistry at The University of Georgia. Professor Robinson and his research team are studying the unique chemistry of low-oxidation state main group chemical compounds. The goal of this research is to exploit the unique stabilizing effects of organic bases (a class of compounds known as carbenes) on highly reactive main group molecules. For example, important molecules like disilicon (Si2) are only detectable at extremely low temperatures. In contrast, diphosphorus (P2) is typically only detectable at very high temperatures. The Robinson team has developed a means to stabilize molecules like Si2 and P2 (and many others) at room temperature, thus allowing the convenient study of the structure and reactivity of these important molecules. In particular, these researchers recently reported the first stable molecular examples of silicon oxides. This project investigates the synthesis of more ambitious silicon oxides. This chemistry has the potential for us to learn more about the silicon-oxygen interface with possible implications to computer chips and semiconductors. These researchers will also attempt to synthesize molecules containing large silicon and arsenic clusters. This project lies at the heart of main group chemistry, a field of inorganic chemistry that has traditionally received more emphasis in Europe. Outreach activities involving women and traditionally under-represented groups is central to this research. The students engaged in this work are acquiring valuable synthetic and experimental skills that make them highly valuable in the employment market.An ambitious program to explore challenging areas of low-oxidation main group chemistry is underway. The Robinson laboratory has developed N-heterocyclic carbenes (NHC or L:) and N-heterocyclic dicarbene (NHDC) derivatives that are being used as a unique platform from which many unusual low-oxidation state main group species can be synthetically stabilized. Major synthetic goals in this work include: (a) carbene-based multisilylenes; (b) carbene-stabilized silicon atom and clusters; (c) carbene-stabilized heteronuclear diatomic molecules [i.e., silicon carbides, diatomic III-V (13-15) species, arsenic phosphide (AsP)]. The recent report by this laboratory of carbene-stabilization of elusive silicon oxides (Nature Chem. 2015, 7, 509) has encouraged these workers to develop the long-sought molecular chemistry of SOx. Consequently, the syntheses of a series of carbene-stabilized silicon oxides (such as SiO, SiO2, Si2O, Si2O2, and Si3O6, etc.) and silicon hydrides [Si3H2 and Si2H2 (parent disilyne)] are being pursued. These carbene-stabilized silicon oxides may be further utilized to develop the corresponding transition-metal-modified derivatives and transfer silicon oxide clusters into organic or organometallic substrates. In addition, carbene-stabilized bis-silylenes are explored as potential transfer agents for the disilyne unit. The transition metal chemistry of carbene-stabilized zero-oxidation-state main group species are being examined in the work. Research findings from the Robinson laboratory have repeatedly challenged traditional theories of structure and bonding in inorganic chemistry and some of this has begun to appear in chemistry textbooks. Students engaged in this work are acquiring valuable synthetic, crystallographic, and computational skills. The Robinson laboratory has a positive record of extending the chemistry enterprise to larger segments of the human resource as a number of women and African Americans have been trained in his laboratory. In addition, Professor Robinson has developed a popular seminar course entitled "Molecules That Changed History".