在线阅读 --自然科学版 2020年4期《取代基对苯并噻吩芳香性的影响》
取代基对苯并噻吩芳香性的影响--[在线阅读]
米金辉, 靳志唯, 李晓艳
河北师范大学 化学与材料科学学院, 河北 石家庄 050024
起止页码: 329--334页
DOI: 10.13763/j.cnki.jhebnu.nse.2020.04.008
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.

Influence of Substituent on the Aromaticity of Benzothiophene
MI Jinhui, JIN Zhiwei, LI Xiaoyan
College of Chemistry and Material Science, Hebei Normal University, Hebei Shijiazhuang 050024, China
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.

收稿日期: 2019-12-17
基金项目: 国家自然科学基金(21973027);河北省教育厅重点科学基金(ZD2018066);河北师范大学研究生创新项目(CXZZSS2019051)

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