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.

有了这一奖项，有机和大分子化学计划支持了巴黎圣母院的化学与生物化学系教授的作品。 这项研究将继续对碳氢化合物自由基阳离子化学的实验和计算研究，这是一类反应性中间体，这些中间体具有新的科学见解和应用潜力。 通过电子转移形成的自由基阳离子通常比中性的反应更快。反电子转移后，这导致了一种非常有效的方法，可以通过电子转移催化加速反应。 立体化学和同位素效应研究将用于阐明这些反应的机械细节，这些详细信息通常由中性对应物中不存在的因素控制或不那么重要。 将研究极性促进自由基阳离子形成的离子液体中电子转移反应的反应性和选择性。 这些实验研究将与反应动力学的高级量子机械计算相辅相成。 这些研究将产生基本信息，这些信息将提供控制电子转移催化的手段，并促进其在现代合成有机化学中的应用。 这种基本知识对于将该技术应用于化学，生物学和材料科学领域至关重要。