烯丙位化学键均裂离解能及其取代基效应HomolyticBond-OALib.PDF

2005 年第 25 卷 有 机 化 学 Vol. 25, 2005 第 11 期, 1398～1402 Chinese Journal of Organic Chemistry No. 11, 1398～1402 ·研究论文· 烯丙位化学键均裂离解能及其取代基效应 王毅敏 周 畅 傅 尧 刘 磊 郭庆祥* ( 中国科学技术大学化学系 合肥 230026) 摘要 使用复合从头算方法系统地获得了一批精确的烯丙位化学键的均裂裂解能(BDE). 取代基效应的研究表明, C— H 与 Si—H 的 BDE 表现出差的 Hammett 关系, 而 N—H, O—H, P—H 与 S—H 的 BDE 表现出好的 Hammett 关系. 进一 步分析表明烯丙位 BDE 受共轭效应比诱导/场效应的影响更为明显. 并且还讨论了 BDE 的基态效应和自由基效应, 其 结果与最近报道的有关苄位 BDE 的结果基本一致. 关键词 键能; G3; CBS-Q; 取代基效应 Homolytic Bond Dissociation Energies of Allylic Compounds and Related Substituent Effects WANG, Yi-Min ZHOU, Chang FU, Yao LIU, Lei GUO, Qing-Xiang* (Department of Chemistry , University of Science and Technology of China, Hefei 230026) Abstract Reliable bond dissociation energies (BDE) of various allylic compounds were obtained using compound methods. It was found that the C—H and Si—H BDE data display poor Hammett relationships, whereas the N—H, O—H, P—H and S—H BDE ones exhibit good Hammett relationships. It was also found that the resonance effect was more important than the inductive/field effect on the allylic BDE. In addition, the ground state and radical state effects on BDE were analyzed. All the results in the present study are in good agreement with our recent results about the benzylic BDE. Keywords bond dissociation energy; G3; CBS-Q; substituent effect 化学键均裂离解能(BDE, bond dissociation energy) 最 近 逐 渐 发 展 并 成 熟 的 复 合 从 头 算 方 法 (compound 通常定义为标准大气压下气态反应(X—Y→X• ＋Y•) 的 methods), 使得我们能够在理论计算中达到化学精度 焓变值[1]. 它是反应热力学、反应动力学以及物理有机