Structure-Reactivity Relationships in Fluorinated and Charged Radical Systems

氟化和带电自由基体系中的结构-反应性关系

• 批准号: 9982587
• 负责人: William Dolbier
• 金额: --
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-02-01 至 2003-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9982587&HistoricalAwards=false
• 关键词: Structure; Reactivity; Relationships; Fluorinated; Charged

With this award the Organic and Macromolecular Chemistry Program renews its support for the work of Dr. William R. Dolbier of the Department of Chemistry at the University of Florida in Gainesville. The major purpose of the work is to build on the discoveries made with earlier NSF funding in the physical organic chemistry of organic molecules containing fluorine, and to develop applications in the areas of organic synthesis, industrial polymers, and biochemistry. Dr. Dolbier will also be investigating the reactions of distonic radical cations, species with an unpaired electron and a positive electrical charge on different atoms in the same molecule. The combination of synthesis, kinetic and mechanistic studies, and theoretical chemistry will provide excellent training for the postdoctoral and graduate students who will work on the project. It should be mentioned that Dr. Dolbier was this year's winner of the ACS Award for Creative Work in Fluorine Chemistry.The work falls into four general radical reaction classes: C-H transfer, cyclizations, cyclopropylcarbinyl ring opening, and reactions of distonic radical cations. Both relative and absolute rate constants are measured after generating the radicals by fast flash photolysis - developing useful correlations between structure and reactivity that can be used to make predictions for molecules where the kinetic data are unavailable.

通过这个奖项，有机和大分子化学项目再次支持盖恩斯维尔佛罗里达大学化学系William R. Dolbier博士的工作。这项工作的主要目的是建立在美国国家科学基金会早期资助的含氟有机分子的物理有机化学发现的基础上，并开发在有机合成、工业聚合物和生物化学领域的应用。多比尔博士还将研究双离子自由基阳离子的反应，即在同一分子中不同原子上带有未配对电子和正电荷的阳离子。综合、动力学和机理研究以及理论化学的结合将为参与该项目的博士后和研究生提供良好的培训。应该提到的是，Dolbier博士是今年美国化学学会氟化学创造性工作奖的获得者。功可分为四类自由基反应：碳氢转移反应、环化反应、环丙基开环反应和双离子自由基阳离子反应。在快速闪光光解生成自由基后，测量相对速率常数和绝对速率常数——在结构和反应性之间建立有用的相关性，可用于预测无法获得动力学数据的分子。