Structure, Reactivity and Selectivity of Hydrocarbon Radical Cations

烃自由基阳离子的结构、反应性和选择性

• 批准号: 0415344
• 负责人: Olaf Wiest
• 金额: $ 34.8万
• 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: 2004
• 资助国家: 美国
• 起止时间: 2004-07-15 至 2008-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0415344&HistoricalAwards=false
• 关键词: Structure; Reactivity; Selectivity; Hydrocarbon; Radical

With this award, the Organic and Macromolecular Chemistry Program supports the work of Professor Olaf G. Wiest of the Department of Chemistry and Biochemistry at the University of Notre Dame, Notre Dame, IN. The research will continue the PI's experimental and computational investigations of the chemistry of hydrocarbon radical cations, a class of reactive intermediates that have significant potential for new scientific insights and applications. Radical cations, which are formed through electron transfer, typically react many orders of magnitude faster than their neutral counterparts. After back electron transfer, this results in a very effective method for the acceleration of reactions through electron transfer catalysis. Stereochemical and isotope effect studies will be used to elucidate the mechanistic details of these reactions that are often controlled by factors absent or less important in their neutral counterparts. The reactivity and selectivity of electron transfer reactions in ionic liquids, in which polarity facilitates radical cation formation, will be investigated. These experimental studies will be complemented by high-level quantum mechanical calculations of reaction dynamics. These investigations will yield basic information that will provide the means to control electron transfer catalysis and facilitate its application in modern synthetic organic chemistry. Such fundamental knowledge is essential for the application of this technique to other areas of chemical, biological and material science.

有了这个奖项，有机和高分子化学计划支持教授奥拉夫G。美国印第安纳州圣母大学化学和生物化学系的Wiest博士说。 该研究将继续PI对碳氢化合物自由基阳离子化学的实验和计算研究，这是一类具有新科学见解和应用潜力的活性中间体。 通过电子转移形成的自由基阳离子通常比它们的中性对应物反应快许多数量级。在反向电子转移之后，这导致通过电子转移催化加速反应的非常有效的方法。 立体化学和同位素效应的研究将被用来阐明这些反应的机理细节，这些反应往往是由不存在或不太重要的因素在其中性对应控制。 离子液体中的电子转移反应的反应性和选择性，其中极性促进自由基阳离子的形成，将进行研究。 这些实验研究将由反应动力学的高级量子力学计算来补充。 这些研究将产生基本的信息，将提供手段来控制电子转移催化和促进其在现代合成有机化学中的应用。 这些基础知识对于将该技术应用于化学、生物和材料科学的其他领域至关重要。