| Sn(OTf)_2催化活化D-A环丙烷的密度泛函研究(英文) |
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| 引用本文： | 张金生,李勇,陈卓,杜海军.Sn(OTf)_2催化活化D-A环丙烷的密度泛函研究(英文)[J].贵州师范大学学报(自然科学版),2007,25(3):93-97. |
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| 作者姓名： | 张金生 李勇 陈卓 杜海军 |
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| 作者单位： | 1. 贵州师范大学,理学院,贵州,贵阳,550001
2. 贵州民族学院,环境与科学学院,贵州,贵阳,550025 |
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| 摘 要： | 用量子化学密度泛函理论对路易斯酸Sn(OTf)2催化活化供电子-吸电子环丙烷的机理进行了量子化学研究.在B3LYP/6-31G计算水平全优化了反应势能面上所有驻点的几何结构,用自洽反应场极化连续介质模型分别在B3LYP/6-31G和B3LYP/6-311G(d,p)计算水平计算了单点溶剂化效应.结果表明,Sn(OTf)2催化活化D-A环丙烷是通过它们的配位作用增大C1-C(2)偶极矩和降低反键轨道σ*(C1-C2)的能量来实现的
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| 关 键 词： | 密度泛函理论(DFT) Sn(OTf)2 供电子-吸电子环丙烷 催化活化 |
| 文章编号： | 1004-5570（2007）03-0093-05 |
| 收稿时间： | 2007-04-28 |
| 修稿时间： | 2007年4月28日 |
Density function theory study on the Sn(OTf)2-catalyzed D-A cyclopropane activation |
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| ZHANG Jin-sheng,Li Yong,CHEN Zhuo,DU Hai-jun.Density function theory study on the Sn(OTf)2-catalyzed D-A cyclopropane activation[J].Journal of Guizhou Normal University(Natural Sciences),2007,25(3):93-97. |
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| Authors: | ZHANG Jin-sheng Li Yong CHEN Zhuo DU Hai-jun |
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| Institution: | 1.School of Physics and Chemistry, Guizhou Normal University, Guiyang, 550001, China; 2.College of Environment and Science, Guizhou College for Nationalities, Guiyang, Guizhou 550025, China |
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| Abstract: | The activation mechanism of Sn(OTf)2-catalyzed Donor-Acceptor (D-A) cyclopropane bearing a malonyl diester accepter group and carbon based resonance donor substituent has been investigated by using density function theory. The geometries for all the stationary points were fully optimized at the B3LYP/6-31G level and the solvent effects were explored by single-point calculations at the B3LYP/6-311G(d,p) level with polarizable continuum model (PCM). The activation mechanism of Sn(OTf)2 catalyzed D-A cyclopropane is suggested to be the increase of σ(C1-C2) bond dipole moment and the decrease of natural bond orbital (NBO) energy of σ*(C1-C2) due to the Sn(II) ion coordination with the D-A cyclopropane, thus the D-A cyclopropane exhibits ambiphilic behavior and σ(C1-C2) is apt to cleavage in the cycloaddition reactions. |
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| Keywords: | DFT Sn(OTf)2 D-A cyclopropane catalyzed activation |
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