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Substituent effects and aromaticity of six-membered heterocycles

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Abstract

Structure, aromaticity, relative stability, and conformational flexibility of nitro and amino substituted monoheterocyclic analogous of benzene were studied by ab initio quantum-chemical method at MP2/aug-cc-pvDZ level of theory. Amino derivatives were found to be slightly less aromatic than nitro derivatives. Strong push–pull interactions were found in α- and γ-aminochalcogenopyrylium cations and, in less extent, in α- and γ-aminopyrydines. These molecules are less aromatic but more stable, as compare to their β-isomers. All heterocycles with 3rd and 4th row heteroatoms reveal C–NO2 bond elongation accompanied by C–Heteroatom bond shortening in β-nitro isomers, and strong inequality of two endocyclic C–Heteroatom bonds in α-amino isomers.

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Authors and Affiliations

  1. STC ‘Institute for Single Crystals’, National Academy of Sciences of Ukraine, 60 Lenina ave., Kharkiv, 61001, Ukraine

    Irina V. Omelchenko & Oleg V. Shishkin

  2. V. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv, 61077, Ukraine

    Oleg V. Shishkin

  3. Badger Technical Services LLC, Vicksburg, MS, USA

    Leonid Gorb

  4. US Army ERDC, 3532 Manor Dr, Vicksburg, MS, 39180, USA

    Frances C. Hill & Jerzy Leszczynski

  5. Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, 1325 Lynch Street, P.O. Box 17910, Jackson, MS, 39217, USA

    Jerzy Leszczynski

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  1. Irina V. Omelchenko
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  2. Oleg V. Shishkin
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  3. Leonid Gorb
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  4. Frances C. Hill
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  5. Jerzy Leszczynski
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Correspondence to Irina V. Omelchenko.

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Omelchenko, I.V., Shishkin, O.V., Gorb, L. et al. Substituent effects and aromaticity of six-membered heterocycles. Struct Chem 24, 725–733 (2013). https://doi.org/10.1007/s11224-012-0124-x

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  • DOI: https://doi.org/10.1007/s11224-012-0124-x

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