Structure-Reactivity Relationships in Fluorinated and Charged Radical Systems

有了这个奖项，有机和高分子化学计划重申其对威廉R。位于盖恩斯维尔的佛罗里达大学化学系的多尔比耶说。 这项工作的主要目的是建立在早期NSF资助的含氟有机分子的物理有机化学发现的基础上，并开发有机合成，工业聚合物和生物化学领域的应用。 Dolbier博士还将研究distonic自由基阳离子的反应，在同一分子中的不同原子上具有未成对电子和正电荷的物质。 合成，动力学和机理研究，以及理论化学的结合将为将从事该项目的博士后和研究生提供良好的培训。 值得一提的是，Dolbier博士是今年ACS氟化学创新工作奖的赢家。该工作福尔斯分为四个一般的自由基反应类别：C-H转移，环化，环丙基卡宾开环和二阶自由基阳离子反应。 在通过快速闪光光解产生自由基后测量相对和绝对速率常数-在结构和反应性之间建立有用的相关性，这些相关性可用于预测动力学数据不可用的分子。

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.