Relative Radical Stabilization Energies

在有机动力学项目的支持下，博德威尔博士将开发估算键解离能（BDEs）大小的新方法。这些研究有望对bde的相对大小和相应的自由基稳定能（RSEs）提供定量估计，这些物质是由氢和其他原子之间的键均裂形成的。他的工作将首次为大量自由基的相对rse大小提供定量估计。同时，这些测量将有助于扩展以二甲亚砜为基础的酸度量表，该量表提供了阴离子碱度的定量测量，并通过Bronsted方程提供了它们对亲电试剂的反应性。对称为“键解离能”的能量的了解，对于寻求发展基本结构-活性关系的物理有机化学家来说，这些基本结构-活性关系可以用来预测给定分子中单个化学键对特定试剂的反应性。反过来，这些信息可以被合成有机化学家用于开发新的合成策略。

With support from the Organic Dynamics Program, Dr. Bordwell will develop new methods for estimating the magnitudes of bond dissociation energies (BDEs). These studies are expected to provide quantitative estimates of the relative magnitudes of BDEs and the corresponding radical stabilization energies (RSEs) for the species that are formed upon homolytic cleavage of bonds between hydrogen and other atoms. His work will provide the first quantitative estimates of the relative magnitudes of RSEs for a large number of radicals. At the same time, these measurements will serve to extend the dimethylsulfoxide-based acidity scale, which provides quantitative measures of anion basicities and, through the Bronsted equation, their reactivities toward electrophiles. %%% Knowledge of the energies, called "bond dissociation energies", that are required to cleave particular chemical bonds is important to physical-organic chemists who seek to develop fundamental structure-activity relationships that can be used to predict the reactivities of individual chemical bonds in a given molecule toward a particular reagent. This information, in turn, can be used by synthetic organic chemists in developing new synthetic strategies.