Chemistry of Deltahedral Zintl Ions and their Organically-Functionalized Derivatives

三角 Zintl 离子及其有机官能化衍生物的化学

• 批准号: 0742365
• 负责人: Slavi Sevov
• 金额: $ 34.5万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-02-01 至 2012-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0742365&HistoricalAwards=false
• 关键词: Chemistry; Deltahedral; Zintl; Ions; their

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Slavi Sevov at Notre Dame University on the reactivity of main-group deltahedral clusters (Zintl ions), both homo- and hetero-atomic (including a number of recently discovered bismuth/transition metal species). Using a variety of organic halides and alkynes, a variety of organic groups will be added to nine-atom germanium clusters [Ge9]n- (n = 4, 3, 2). The products of these reactions are mono- and di-substituted clusters [R-Ge9]3- and [R-Ge9-R]2-, respectively, where the R groups can be simple alkyl groups or can have double bonds, phenyl or pyridine rings, and other functionalities. These studies will be extended into the other elements of this group, which form the same nine-atom clusters, i.e. [Si9]n-, [Sn9]n-, and [Pb9]n-, as well as into heteroatomic clusters such as ([Ge9]-x[Snx])n-, (In4Bi5)3-, and (Tl4Bi5)3-. The proposed reactions focus on the organic substituents and take advantage of well-studied reactions in other areas of chemistry such as organic and organometallic chemistry by applying the accumulated knowledge to the new substrates. For example, the double bonds in alkenyl-Zintl ions such as [CH2=CH-Ge9-CH=CH2]2- may be susceptible to hydroboration and/or polymerization. Pyridine-substituted Zintl ions may be able to coordinate to transition metals via the pyridine nitrogen and to form molecular or extended structures. The relation between the geometry and bonding of small molecular clusters, and their properties and reactivity will be investigated. The proposed clusters are of interest as potential precursors to new classical materials (intermetallics, extended structures) as well as nano materials (nanorods, thin films, surface grafting) with novel electronic and magnetic properties. The project will be used as a tool to attract both students and postdoctoral fellows from underrepresented groups through a relationship with the Graduate Education for Minorities organization. Relationships are also being developed with the predominantly minority Clark University (Atlanta), Xavier (New Orleans), and St. Mary and St. Edward colleges (San Antonio) in order to bring summer undergraduate students and to recruit graduate students from these universities.

这个无机、生物无机和有机金属化学项目的奖项支持圣母大学的Slavi Sevov教授对主基团三角面体簇（锌离子）的反应性的研究，包括同原子和异原子（包括一些最近发现的铋/过渡金属物种）。利用多种有机卤化物和炔，将多种有机基团添加到九原子锗团簇[Ge9]n- (n = 4,3,2)上。这些反应的产物分别是单取代簇和双取代簇[R- ge9]3-和[R- ge9 -R]2-，其中R基团可以是简单的烷基，也可以具有双键、苯基或吡啶环和其他官能团。这些研究将扩展到该组的其他元素，它们形成相同的九原子簇，即[Si9]n-， [Sn9]n-和[Pb9]n-，以及杂原子簇，如（[Ge9]-x[Snx]）n-, (In4Bi5)3-和（Tl4Bi5）3-。提出的反应侧重于有机取代基，并利用其他化学领域（如有机化学和有机金属化学）中已经得到充分研究的反应，将积累的知识应用于新的底物。例如，烯基锌离子（如[CH2=CH-Ge9-CH=CH2]2-）中的双键可能容易发生硼氢化和/或聚合。吡啶取代的锌离子可以通过吡啶氮与过渡金属配位并形成分子或扩展结构。研究了小分子簇的几何形状和成键之间的关系，以及它们的性质和反应性。所提出的团簇是具有新型电子和磁性能的新型经典材料（金属间化合物，扩展结构）以及纳米材料（纳米棒，薄膜，表面接枝）的潜在前体。该项目将作为一种工具，通过与少数民族研究生教育组织的关系，从代表性不足的群体中吸引学生和博士后。为了从这些大学引进暑期本科生和招收研究生，我们还与少数族裔占主导地位的克拉克大学（亚特兰大）、泽维尔大学（新奥尔良）和圣玛丽和圣爱德华学院（圣安东尼奥）建立了关系。