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

Irina V Omelchenko, Oleg V Shishkin, Leonid Gorb, Jerzy Leszczynski, Stijn Fias UGent and Patrick Bultinck UGent (2011) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 13(46). p.20536-20548
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".
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
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
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Phys. Chem. Chem. Phys.
volume
13
issue
46
pages
20536 - 20548
Web of Science type
Article
Web of Science id
000297071400003
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.573 (2011)
JCR rank
5/32 (2011)
JCR quartile
1 (2011)
ISSN
1463-9076
DOI
10.1039/c1cp20905a
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1972640
handle
http://hdl.handle.net/1854/LU-1972640
date created
2011-12-22 09:19:58
date last changed
2018-01-29 12:12:59
@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},
}

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.