Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study
Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study
复制标题
DOI：
10.1002/chem.201901439
复制
发表时间：
2019-07-05
影响因子：
4.3
通讯作者：
Klussmann, Martin
中科院分区：
文献类型：
--
作者：
Verschueren, Rik H.;Schmauck, Julie;Klussmann, Martin
在这项工作中，丙酮基和苯甲酰基自由基的反应活性的芳香族取代和加成反应进行了比较，在实验和计算研究。结果表明，丙酮基比苯甲酰基更亲电，而苯甲酰基更亲核。Hammett图分析表明苯甲酰基具有亲核性，而丙酮基则没有发现与取代基相关的线性关系，计算结果有助于解释这种效应。并且发现极性参数（σ（+））和所形成中间体的自由基稳定化能的组合具有良好的线性相关性。基于计算的亲合指数苯甲酰基和丙酮基，这两个自由基与许多其他报道的自由基的定量比较是可能的，这可能有助于预测其他芳香族自由基取代反应的反应性。
In this work, the reactivities of acetonyl and benzoyl radicals in aromatic substitution and addition reactions have been compared in an experimental and computational study. The results show that acetonyl is more electrophilic than benzoyl, which is rather nucleophilic. A Hammett plot analysis of the addition reactions of the two radicals to substituted styrenes clearly support the nucleophilicity of benzoyl, but in the case of acetonyl, no satisfactory linear correlation with a single substituent-related parameter was found. Computational calculations helped to rationalize this effect, and a good linear correlation was found with a combination of polar parameters (sigma(+)) and the radical stabilization energies of the formed intermediates. Based on the calculated philicity indices for benzoyl and acetonyl, a quantitative comparison of these two radicals with many other reported radicals is possible, which may help to predict the reactivities of other aromatic radical substitution reactions.