Aromaticity and conformational flexibility of five-membered monoheterocycles: pyrrole-like and thiophene-like structures
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- 作者：Irina V. Omelchenko ; Oleg V. Shishkin ; Leonid Gorb…
- 关键词：Aromaticity ; Five ; membered heterocycles ; Aromaticity indices ; Aromatic ring flexibility
- 刊名：Structural Chemistry
- 出版年：2016
- 出版时间：February 2016
- 年：2016
- 卷：27
- 期：1
- 页码：101-109
- 全文大小：678 KB
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Oleg V. Shishkin (1) (2)
Leonid Gorb (3)
Jerzy Leszczynski (4) (5)
1. SSI ‘Institute for Single Crystals’, National Academy of Sciences of Ukraine, 60 Lenin Ave., Kharkiv, 61001, Ukraine
2. V.N.Karazin Kharkiv National University, 4 Svobody Sq., Kharkiv, 61077, Ukraine
3. Badger Technical Services, LLC, Vicksburg, MS, USA
4. US Army ERDC, 3532 Manor Dr, Vicksburg, MS, 39180, USA
5. Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, P.O. Box 17910, 1325 Lynch Street, Jackson, MS, 39217, USA - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Computer Applications in Chemistry
Physical Chemistry
Theoretical and Computational Chemistry - 出版者：Springer Netherlands
- ISSN：1572-9001
文摘
Aromaticity and conformational flexibility of the series of five-membered monoheterocycles with group 14–16 heteroatoms, having one or two lone pairs, were studied with ab initio methods using NICS, ASE and I 5 indices. For non-planar molecules like phosphole, aromaticity of their planar transition states was also studied, and a special modification of ASE index was proposed to that end. It was found that the presence of two lone pairs is generally preferable for aromaticity of all heterocycles except CPD and silolyl dianions. Heterocycles with group 16 heteroatoms have consistently lower aromaticity compared to other groups. A lot of structures should be classified as moderate aromatic and non-aromatic. Energies of out-of-plane deformation do not correlate with other indices studied, but reveal the same qualitative trends. Generally, aromaticity of five-membered monoheterocycles depends strongly on both heteroatom type and number of lone pairs on it. Keywords Aromaticity Five-membered heterocycles Aromaticity indices Aromatic ring flexibility