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Aromaticity in heterocyclic analogues of benzene : comprehensive analysis of structural aspects, electron delocalization and magnetic characteristics

(2011) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 13(46). p.20536-20548
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
The degree of aromaticity of six-membered monoheterocycles with IV-VI group heteroatoms (C(6)H(5)X, where X = SiH, GeH, N, P, As, O(+), S(+), Se(+)) was analyzed using the results of ab initio calculations at the MP2/cc-pvtz level. Values of common aromaticity indices including those based on electronic delocalization properties, structural-dynamic features and magnetic properties all indicate high aromaticity of all considered heterocycles. A decrease in aromaticity is observed with increasing atomic number of the heteroatom, except in the case of the pyrylium cation. However, not all types of indices or even different indices within the same type correlate well among each other. Ring currents have been obtained at the HF/cc-pvdz level using the ipsocentric formulation. Ring current maps indicate that in the case of cationic heterocycles the ring current persists in all molecules under consideration. The different conclusions reached depending on the type of index used are a manifestation of the fact that when not dealing with hydrocarbons, aromaticity is ill-defined. One should always express explicitly which property of the molecules is considered to establish a degree of "aromaticity".
Keywords
RING CRITICAL-POINTS, INDEPENDENT CHEMICAL-SHIFTS, ring currents, six-membered heterocycles, conformational flexibility, aromaticity index, aromaticity, MULTICENTER BOND INDEXES, CURRENT-DENSITY, STABILIZATION ENERGIES, AB-INITIO, CONFORMATIONAL FLEXIBILITY, CONTINUOUS TRANSFORMATION, TOPOLOGICAL ENVIRONMENTS, MOLECULAR SIMILARITY

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Citation

Please use this url to cite or link to this publication:

Chicago
Omelchenko, Irina V, Oleg V Shishkin, Leonid Gorb, Jerzy Leszczynski, Stijn Fias, and Patrick Bultinck. 2011. “Aromaticity in Heterocyclic Analogues of Benzene : Comprehensive Analysis of Structural Aspects, Electron Delocalization and Magnetic Characteristics.” Physical Chemistry Chemical Physics 13 (46): 20536–20548.
APA
Omelchenko, I. V., Shishkin, O. V., Gorb, L., Leszczynski, J., Fias, S., & Bultinck, P. (2011). Aromaticity in heterocyclic analogues of benzene : comprehensive analysis of structural aspects, electron delocalization and magnetic characteristics. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13(46), 20536–20548.
Vancouver
1.
Omelchenko IV, Shishkin OV, Gorb L, Leszczynski J, Fias S, Bultinck P. Aromaticity in heterocyclic analogues of benzene : comprehensive analysis of structural aspects, electron delocalization and magnetic characteristics. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2011;13(46):20536–48.
MLA
Omelchenko, Irina V, Oleg V Shishkin, Leonid Gorb, et al. “Aromaticity in Heterocyclic Analogues of Benzene : Comprehensive Analysis of Structural Aspects, Electron Delocalization and Magnetic Characteristics.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 13.46 (2011): 20536–20548. Print.
@article{1972640,
  abstract     = {The degree of aromaticity of six-membered monoheterocycles with IV-VI group heteroatoms (C(6)H(5)X, where X = SiH, GeH, N, P, As, O(+), S(+), Se(+)) was analyzed using the results of ab initio calculations at the MP2/cc-pvtz level. Values of common aromaticity indices including those based on electronic delocalization properties, structural-dynamic features and magnetic properties all indicate high aromaticity of all considered heterocycles. A decrease in aromaticity is observed with increasing atomic number of the heteroatom, except in the case of the pyrylium cation. However, not all types of indices or even different indices within the same type correlate well among each other. Ring currents have been obtained at the HF/cc-pvdz level using the ipsocentric formulation. Ring current maps indicate that in the case of cationic heterocycles the ring current persists in all molecules under consideration. The different conclusions reached depending on the type of index used are a manifestation of the fact that when not dealing with hydrocarbons, aromaticity is ill-defined. One should always express explicitly which property of the molecules is considered to establish a degree of {\textacutedbl}aromaticity{\textacutedbl}.},
  author       = {Omelchenko, Irina V and Shishkin, Oleg V and Gorb, Leonid and Leszczynski, Jerzy and Fias, Stijn and Bultinck, Patrick},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keyword      = {RING CRITICAL-POINTS,INDEPENDENT CHEMICAL-SHIFTS,ring currents,six-membered heterocycles,conformational flexibility,aromaticity index,aromaticity,MULTICENTER BOND INDEXES,CURRENT-DENSITY,STABILIZATION ENERGIES,AB-INITIO,CONFORMATIONAL FLEXIBILITY,CONTINUOUS TRANSFORMATION,TOPOLOGICAL ENVIRONMENTS,MOLECULAR SIMILARITY},
  language     = {eng},
  number       = {46},
  pages        = {20536--20548},
  title        = {Aromaticity in heterocyclic analogues of benzene : comprehensive analysis of structural aspects, electron delocalization and magnetic characteristics},
  url          = {http://dx.doi.org/10.1039/c1cp20905a},
  volume       = {13},
  year         = {2011},
}

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