氮苄叉基苯胺及其衍生物的构象

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (2): 308.

氮苄叉基苯胺及其衍生物的构象

徐红, 虞忠衡

中国科学院化学研究所, 分子动态与稳态结构国家重点实验室, 北京 100080

收稿日期:2004-02-23 出版日期:2005-02-10 发布日期:2005-02-10
通讯作者: 虞忠衡(1944年出生),男,博士,研究员,博士生导师,主要从事物理有机化学的研究.E-mail:yuzh@iccas.ac.cn E-mail:yuzh@iccas.ac.cn
基金资助:
国家自然科学基金(批准号:2047208,20276023,20032010)资助

N-Benzylideneaniline-like Derivatives and Their Conformation

XU Hong, YU Zhong-Heng

State Key Laboratory of Stable and Unstable Species, Institute of Chemistry,Chinese Academy of Sciences, Beijing 100080, China

Received:2004-02-23 Online:2005-02-10 Published:2005-02-10

摘要/Abstract

摘要： 为了探索氮苄叉基苯胺及其衍生物产生大扭角构象的根本原因,对21个分子分别在HF/6-311G^**和B3LYP/6-311G^**水平下进行了全优化和近似的势能面扫描.结果显示,分子扭曲的驱动力源于分子内的电子相互作用,片段间的核排斥作用是分子扭曲的阻力.经B3LYP/6-311G^**势能面扫描后,分别用HF,BLYP,BVWN,B3LYP和MP2法在不同的基组下对各旋转构象再作单点能运算.在简单的NBA分子中,STO-3G可以足够精确地描述分子扭曲的驱动力,但是它不能很好地描述分子内的氢键效应.

关键词: 扭曲驱动力, 构象, 氮苄叉基苯胺

Abstract: To discern the driving force for distorting the geometry of NBA-like species, the relax potential energy scan was performed at the B3LYP/6-311G ^** level, for each molecule of 21 NBA-like species substituted with typical electron donor and/or acceptor at their benzylidene, aniline, and/or imine groups. In general, it is electron interaction, rather than nuclear repulsion between fragments, to distort a molecule away from its planar geometry, and their lowest total electronic energies occur in the geometries with the similar twist angles about 50°. Afterwards, the single point energies for 21 rotational geometries of each of two typical molecules 1 and 17 are calculated by using HF, BLYP, BVWN, B3LYP and MP2 at various Gaussian basis levels. Interestingly, STO-3G is accurate enough to understand the driving force for distorting NBA away from its planar geometry, but it is unreasonable to describe the intra-molecular hydrogen bond.

Key words: Driving force for distorting, Conformation, N-Benzylideneanilines

中图分类号:

O626
O641

TrendMD:

徐红, 虞忠衡. 氮苄叉基苯胺及其衍生物的构象. 高等学校化学学报, 2005, 26(2): 308.

XU Hong, YU Zhong-Heng. N-Benzylideneaniline-like Derivatives and Their Conformation. Chem. J. Chinese Universities, 2005, 26(2): 308.

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