Synthesis and Redox Chemistry of Tetrachalcogenotetraasteranes

四硫属元素四甾烷的合成和氧化还原化学

• 批准号: 0201555
• 负责人: Richard Glass
• 金额: $ 2.89万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-01 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0201555&HistoricalAwards=false
• 关键词: Synthesis; Redox; Chemistry; Tetrachalcogenotetraasteranes

Professor Glass will lead a collaborative project involving the research groups of Professor Potapov (Irkutsk, Russia) and Professor Glass (Tucson, AZ, USA) on the synthesis and redox chemistry of tetrachalcogentetraasteranes (sulfur, selenium and tellurium) is proposed. The synthesis of these "star-shaped" molecules is based on the photodimerization of 1,4-dichalcogenins. The oxidation of these materials will be studied using the electrochemical technique of cyclic voltammetry and chemical oxidants. One-electron oxidation of these compounds may provide stable radical cations with novel structures in which the charge and the odd electron are delocalized equally over all four chalcogen atoms. Spectroscopic methods, especially EPR spectroscopy, are proposed for determining the structures of these materials. Two-electron oxidation of the heteroatom asteranes will be investigated to evaluate the theory of a-aromaticity. The dications may show unusual properties if they are a-delocalized. This possibility will be evaluated by spectroscopic methods, especially NMR spectroscopy. This proposed collaborative work combines the research strengths of Professor Potapov's group in synthetic heteroatom chemistry with that of Professor Glass' group in structural and redox chemistry in a mutually beneficial project which may extend our understanding of multicenter bonding and structural factors that affect electron-transfer.With this Award, The Organic and Macromolecular Chemistry Program and the Central and Eastern Europe Program in the Office of International Science and Engineering will support the research and international collaboration of Professor Richard S. Glass of the University of Arizona.

Glass教授将领导一个由Potapov教授（伊尔库茨克，俄罗斯）和Glass教授（图森，亚利桑那州，美国）研究小组参与的合作项目，研究四乙醇原四甾烷（硫，硒和碲）的合成和氧化还原化学。这些“星形”分子的合成是基于1,4-二硫原的光二聚化。这些材料的氧化将使用循环伏安法和化学氧化剂的电化学技术进行研究。这些化合物的单电子氧化可以提供具有新颖结构的稳定的自由基阳离子，其中电荷和奇电子在所有四个碳原子上均匀地离域。提出了光谱方法，特别是EPR光谱法来测定这些材料的结构。本文将研究杂原子甾烷的双电子氧化反应，以评价a-芳构性理论。如果这些指示符是非局部化的，它们可能会显示出不寻常的性质。这种可能性将通过光谱学方法，特别是核磁共振光谱学来评估。这项合作计划将Potapov教授团队在合成杂原子化学方面的研究优势与Glass教授团队在结构和氧化还原化学方面的研究优势结合起来，这是一个互利的项目，可以扩展我们对多中心键和影响电子转移的结构因素的理解。通过该奖项，国际科学与工程办公室的有机和大分子化学项目以及中欧和东欧项目将支持亚利桑那大学Richard S. Glass教授的研究和国际合作。