| Theoretical Study of Remote Substituent Effects on X-H （X=CH2, NH,O） Bond Dissociation Energies of Azulene |
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| 引用本文： | 俞一赞,傅尧,刘磊,郭庆祥.Theoretical Study of Remote Substituent Effects on X-H （X=CH2, NH,O） Bond Dissociation Energies of Azulene[J].中国化学,2007,25(7):1014-1022. |
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| 作者姓名： | 俞一赞 傅尧 刘磊 郭庆祥 |
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| 作者单位： | Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China （No. 20472079） and Anhui Provincial Natural Science Faundation （No 070416237）. |
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| 摘 要： | In the study, the X-H （X=CH2, NH, O） bond dissociation energies （BDE） of para-substituted azulene （Y-C10H8X-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-CIoHsX-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.
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| 关 键 词： | 甘菊环 取代基效应 粘结离解能量 密度泛函理论 偶极矩 |
| 修稿时间： | 2006-08-042007-03-26 |
Theoretical Study of Remote Substituent Effects on X-H （X=CH2, NH,O） Bond Dissociation Energies of Azulene |
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| YU Yi-Yun,FU Yao, LIU Lei, GUO Qing-Xiang.Theoretical Study of Remote Substituent Effects on X-H （X=CH2, NH,O） Bond Dissociation Energies of Azulene[J].Chinese Journal of Chemistry,2007,25(7):1014-1022. |
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| Authors: | YU Yi-Yun FU Yao LIU Lei GUO Qing-Xiang |
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| Institution: | Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China |
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| Abstract: | In the study, the X–H (X?CH2, NH, O) bond dissociation energies (BDE) of para‐substituted azulene (Y‐C10H8X‐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. |
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| Keywords: | azulene substituent effect bond dissociation energy density functional theory dipole moment |
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