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  • 刊名： 河北师范大学学报（自然科学版）Journal of Hebei Normal University (Natural Science)
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取代基对苯并噻吩芳香性的影响

  • 河北师范大学 化学与材料科学学院, 河北 石家庄 050024
  • DOI： 10.13763/j.cnki.jhebnu.nse.2020.04.008

Influence of Substituent on the Aromaticity of Benzothiophene

摘要/Abstract

摘要：

含金属杂原子的共轭体系因在生物医药、化学反应催化等领域展现出广阔的应用前景而备受关注.过渡金属取代的苯并噻吩是一类重要的反应中间体，同时具有孤对电子和芳香性π电子，因此显示出特殊的性质.在M06-L/aug-cc-pVDZ（过渡金属采用aug-cc-pVDZ-pp）水平上，通过核独立化学位移（NICS）、π轨道及各向异性磁感应电流密度（AICD）等分析，研究了包括过渡金属在内的不同基团取代的苯并噻吩芳香性，讨论了不同种类、不同位置取代对噻吩环芳香性的影响.计算结果表明：苯并噻吩具有很强的芳香性，噻吩环上C3位过渡金属及S位取代基的引入使芳香性明显降低，但C3位取代的金属种类及S原子上取代基变化对芳香性影响较小；C2上连接H原子时，金属取代苯并噻吩为芳香性，连接体积较大的nPr基时为反芳香性.

Abstract：

Metal-atom-containing conjugated systems show broad application in areas of biological medicine and catalyzed chemistry.Transitional metal substituted benzothiophene is an important intermediate,due to the presence of both a lone pair and aromatic π electrons.In this work,the aromaticity of substituted benzothiophenes,including transition metal substitution,has been studied at M06-L/aug-cc-pVDZ(aug-cc-pVDZ-pp for transition metal) level based on nuclear independent chemical shift(NICS),π orbital and anisotropic magnetic induction current density(AICD) analysis,respectively.The influence of different substituents,as well as the different sites of thiophene ring,has been discussed.The results show that the thiophene ring is aromaticity; the aromaticity decreases after the metal substituted at C3 and the substituent adding on S site，while the effects of the kinds of metal on C3 and substituents on S site on the aromaticity are small.As hydrogen atom links to C2,the thiophene ring is aromaticity while it changes to anti-aromaticity when the bulky C3H7 connected to C2.

关键词

关键词： 苯并噻吩 ; 芳香性 ; 取代基 ; 过渡金属 ; 密度泛函理论
Key words： benzothiophene ; aromaticity ; substituent ; transitional metal ; density function theory

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