Structure, Reactivity and Selectivity of Hydrocarbon Radical Cations

通过这一奖项，有机和高分子化学项目支持了印第安纳州圣母大学化学和生物化学系的Olaf G.Wiest教授的工作。这项研究将继续PI对碳氢自由基阳离子化学的实验和计算研究，碳氢自由基阳离子是一类具有巨大潜力的新的科学见解和应用的活性中间体。通过电子转移形成的自由基阳离子的反应速度通常比中性阳离子快许多个数量级。在反向电子转移后，这是一种通过电子转移催化来加速反应的非常有效的方法。立体化学和同位素效应研究将用于阐明这些反应的机理细节，这些反应往往受中性反应中不存在或不太重要的因素控制。将研究离子液体中电子转移反应的反应性和选择性，在离子液体中，极性促进自由基阳离子的形成。这些实验研究将得到反应动力学的高水平量子力学计算的补充。这些研究将为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提供基础信息。这些基础知识对于将这项技术应用于化学、生物和材料科学的其他领域是必不可少的。

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.