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

作　　者：俞一赞 傅尧 刘磊 郭庆祥 

机构地区：[1]Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China

出　　处：《Chinese Journal of Chemistry》2007年第7期1014-1022,共9页中国化学（英文版）

基　　金：Project supported by the National Natural Science Foundation of China （No. 20472079） and Anhui Provincial Natural Science Faundation （No 070416237）.

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.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.

关 键 词：AZULENE substituent effect bond dissociation energy density functional theory dipole moment 

分 类 号：O641.1[理学—物理化学]