New Chemistry of Phosphatrane Bases and of Disilanes

磷川碱和乙硅烷的新化学

• 批准号: 9905354
• 负责人: John Verkade
• 金额: $ 30万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-08-01 至 2003-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9905354&HistoricalAwards=false
• 关键词: New; Chemistry; Phosphatrane; Bases; Disilanes

Professor John Verkade, Chemistry Department, Iowa State University is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for investigations into free radical silicon chemistry and secondary studies of the phosphatrane reactivity. Thermally formed silane free-radicals will be reagents for the formation of aromatic molecules by alkyne cyclotrimerization. A range of alkynes will be investigated to define the range in substituent size and electronic properties that the cyclotrimerization process can tolerate. The possibility of incorporating two different alkynes into the aromatic product and of using various disilanes and other group 14 cogners will be evaluated. A series of disilicon ring systems will be formed by reactions of disilanes with stoichiometric amounts of alkynes and will be used to produce oxygen bridged disilcyclohexandiene polymers. A minor portion of the investigation will target the synthesis of chiral and novel phosphatrane "superbases." Alkyne trimerization is an extremely useful transformation that converts acetylenes into aromatic molecules. The simplest example is the cyclization of acetylene to benzene. Since complex aromatic molecules are found throughout nature and are encountered in many, e.g., pharmaceuticals, new methods for preparing them are very significant. This study will target a class of silicon compounds that can facilitate the trimerization. A set of cyclic molecules that contain two silicon atoms will also be prepared. These will be used as precursors to form new polymers that will be more robust than the silicone polymers, which they resemble.

爱荷华州立大学化学系John Verkade教授得到化学系无机、生物无机和有机金属项目的支持，研究自由基硅化学和磷酸烷反应性的二级研究。热生成的硅烷自由基将成为炔环三聚化生成芳香分子的试剂。将研究一系列炔，以确定取代基尺寸和环三聚化过程可以容忍的电子性质的范围。将评估在芳香产品中加入两种不同炔的可能性，以及使用各种二烷和其他14族化合物的可能性。一系列的二硅环体系将由二硅烷与化学计量量的炔烃反应形成，并将用于生产氧桥接的二二环己二烯聚合物。研究的一小部分将针对手性和新型磷酸烷“超碱”的合成。炔三聚化是一种非常有用的转化，将乙炔转化为芳香分子。最简单的例子是乙炔环化成苯。由于复杂的芳香分子在自然界中随处可见，并且在许多领域（例如药物）中都存在，因此制备它们的新方法非常重要。本研究将针对一类能促进三聚化的硅化合物。一组含有两个硅原子的环状分子也将被制备出来。这些将被用作前体，形成新的聚合物，这种聚合物将比它们相似的硅树脂聚合物更坚固。