| 四同芳香性转烯及其羰基硼衍生物 |
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| 引用本文： | 裴晓琴,武海顺,张晓清,许兴友. 四同芳香性转烯及其羰基硼衍生物[J]. 化学学报, 2007, 65(14): 1357-1362 |
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| 作者姓名： | 裴晓琴 武海顺 张晓清 许兴友 |
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| 作者单位： | 淮海工学院化工系,连云港,222005;山西师范大学化学与材料科学学院,临汾,041004;天津科技大学分析测试中心,天津,300450 |
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| 基金项目： | 国家自然科学基金 , 山西省青年基金 |
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| 摘 要： | 运用G03W程序, 在高精度理论水平(B3P86/6-311＋G**)下, 对母体转烯(Hypostrophene)及其BCO衍生物的单态、三态、开壳层单态的Cope重排体系进行了理论研究: 对体系进行了相应的结构优化和频率计算, 并进一步计算了体系的重排势垒、反应能量、核独立化学位移值等理论参数. 文中首次提出具有四同芳香性的实例: 转烯的Cope重排过渡态. 计算同时表明BCO取代CH的行为使得进行Cope重排的反应物和过渡态的离域性、芳香性以及稳定性都得到很大的促进, 这可以从前线轨道的成键以及延伸方面得到合理的解释. 所得结果进一步验证了BCO基团的稳定性效应.
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| 关 键 词： | 构型 芳香性 反应势垒 分子轨道 |
| 收稿时间： | 2006-10-19 |
| 修稿时间： | 2006-10-192007-03-21 |
Tetrahomoaromatic Hypostrophene and Its BCO-analogues |
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| PEI Xiao-Qin,WU Hai-Shun,ZHANG Xiao-Qing,XU Xing-You. Tetrahomoaromatic Hypostrophene and Its BCO-analogues[J]. Acta Chimica Sinica, 2007, 65(14): 1357-1362 |
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| Authors: | PEI Xiao-Qin WU Hai-Shun ZHANG Xiao-Qing XU Xing-You |
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| Affiliation: | (1 Department of Chemistry and Engineering, Huaihai Institute of Technology, Lianyungang 222005)(2 School of Chemistry and Material Science, Shanxi Normal University, Linfen 041004)(3 Department of Chemistry, Tianjin University of Science & Technology, Tianjin 300450) |
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| Abstract: | Calculations on the normal singlet, triplet and open-shell singlet of hypostrophene, its BCO- analogues and the theoretical transition states for the Cope rearrangement at the B3P86/6-311 G** level have been done with G03W program. By discussing the geometries of the hypostrophene and its BCO-ana- logues, nucleus independent chemical shifts (NICS), the Cope barriers and the molecule orbitals, we got some interesting information. The transition state for the hypostrophene was the first neutral tetra- homoaromaticity case in recent papers. In the hypostrophene system, the replacements of CH by BCO caused theoretical transition states to be delocalized and aromatic energy minimized, resulting in enhance- ment of delocalization, aromaticity and stability of both reactants and transition states, which confirmed the BCO stabilization effects further. |
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| Keywords: | configuration aromaticity reaction barrier molecular orbital |
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