Organosilicon Molecular Assembly, Synthesis, and Electron Transfer

有机硅分子组装、合成和电子转移

• 批准号: 0091162
• 负责人: Joseph Lambert
• 金额: $ 43.78万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-04-15 至 2004-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0091162&HistoricalAwards=false
• 关键词: Organosilicon; Molecular; Assembly; Synthesis; Electron

This proposal describes several problems that involve organic molecules containing silicon, the atom just below carbon in the periodic table. The presence of silicon offers several advantages and, in fact, is the key component of all these problems. First, the high strength of the silicon-oxygen bond enables complex molecules to be self-assembled. Large rings with nanometer-sized cavities are designed to serve as hosts. Molecular recognition of the Si-O bond will demonstrate that organic-silicon compounds can have an interesting and useful aqueous chemistry. A new family of reagents will exert control on reactivity so that a single mirror image product is favored (enantioselectivity). Second, silicon is used to construct new molecular spherical and hemispherical cavities. Cyclodextrins and calixarenes will be attached to an organosilicate network to prepare microporous structures capable of binding with small molecules. An entirely new cavity-containing system that derives from a central silicon atom will be prepared. Third, electron transfer will be characterized along an all-silicon molecular backbone, that is, a silicon wire. This study will be the first attempt to characterize a molecular-sized wire based on an entirely non-carbon pathway. Fourth, new systems will be prepared in which silicon is positively charged and attached to only three other groups (silylium cations). And, fifth, silicon reagents will be used to prepare, at room temperature, new systems containing positively charged carbon (carbocations).With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Joseph B. Lambert of the Department of Chemistry at Northwestern University. Professor Lambert will focus his work on incorporating silicon into normal analogues of carbon compounds or into novel structures to create molecules with potentially important properties. The properties may be of theoretical interest or they may offer new practical applications. The scope of the project is increased by exploiting one of the reactions to devise a new method to add the silicon-hydrogen bond to carbon-carbon double bonds (hydrosilylation) in a process that is catalytic but avoids the use of precious metals necessary in the current process.

该提案描述了涉及含硅有机分子的几个问题，硅是元素周期表中碳下方的原子。硅的存在提供了多种优势，事实上，它是所有这些问题的关键组成部分。首先，硅氧键的高强度使得复杂分子能够自组装。具有纳米尺寸空腔的大环被设计用作主体。 Si-O 键的分子识别将证明有机硅化合物可以具有有趣且有用的水化学。一系列新的试剂将控制反应性，从而有利于单一镜像产物（对映选择性）。其次，硅被用来构建新的分子球形和半球形空腔。环糊精和杯芳烃将附着在有机硅酸盐网络上，以制备能够与小分子结合的微孔结构。将制备一种源自中心硅原子的全新含空腔系统。第三，电子转移将沿着全硅分子主链（即硅线）进行表征。这项研究将是首次尝试表征基于完全非碳途径的分子大小的导线。第四，将制备新系统，其中硅带正电并仅连接到其他三个基团（硅阳离子）。第五，硅试剂将用于在室温下制备含有带正电的碳（碳正离子）的新系统。有机和高分子化学计划通过这一续奖，支持了该大学 Joseph B. Lambert 博士的研究。西北大学化学系。兰伯特教授的工作重点是将硅融入碳化合物的正常类似物或新颖的结构中，以创造具有潜在重要特性的分子。这些特性可能具有理论意义，也可能提供新的实际应用。该项目的范围扩大了，通过利用其中一个反应设计一种新方法，在催化过程中将硅-氢键添加到碳-碳双键上（硅氢加成），但避免使用反应过程中所需的贵金属。当前进程。