Theoretical Study of Remote Substituent Effects on X-H (X=CH2, NH, O) Bond Dissociation Energies of Azulene

• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2007,（7）
• 页码范围: 1014-1022
• 页数: 9页
• 语种: 英文

摘要

In the study, the X-H (X=CH2, NH, O) bond dissociation energies (BDE) of para-substituted azulene (Y-C10HsX-H) were predicted theoretically for the first time using Density Functronal Theory (DFT) methods at UB3LYP/6-311 + +g(2df,2p)//UB3LYP/6-31 +g(d) level. It was found that the substituents exerted similar effects on the X-H BDE of azulene as those on benzene, except for 6-substituted 2-methylazulene. Owing to the substituent-dipole interaction, the reaction constants (ρ+) of 2- and 6-Y-C10H8X-H (X=NH and O only) varied violently. The origin of the substituent effects on the X-H BDE of azulene was found, by both GE/RE and SIE theory,to be directly associated with variation of the radical effects, although the ground effects also played a modest role in determining the net substituent effects.