Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria

Aromaticity is a key concept in physical organic chemistry. The aromatic order of the classic heterobenzenes was reported in experiment early. However, the unambiguous criteria used to validate the aromaticity of that were controversial or inadequate in theory. In this work, the global aromaticity o...

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Main Authors: Hou, B., Yi, P., Wang, Z., Zhang, S., Zhao, J., Mancera, Ricardo, Cheng, Y., Zuo, Z.
Format: Journal Article
Published: Elsevier BV 2014
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/45418
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author Hou, B.
Yi, P.
Wang, Z.
Zhang, S.
Zhao, J.
Mancera, Ricardo
Cheng, Y.
Zuo, Z.
author_facet Hou, B.
Yi, P.
Wang, Z.
Zhang, S.
Zhao, J.
Mancera, Ricardo
Cheng, Y.
Zuo, Z.
author_sort Hou, B.
building Curtin Institutional Repository
collection Online Access
description Aromaticity is a key concept in physical organic chemistry. The aromatic order of the classic heterobenzenes was reported in experiment early. However, the unambiguous criteria used to validate the aromaticity of that were controversial or inadequate in theory. In this work, the global aromaticity of the compounds has been studied using the ELF, NICS and ISE. NICS(max)zz was calculated based on the maximum NICS contribution to the out-of-plane zz tensor component. Two types of bonds are observed. The correlations between NICS(max)σzz and NICS(max)πzz with respect to aromaticity are demonstrated, specifically between NICS(max)πzz and ELFπ (cc = 0.98) for π bonds. For σ bonds, the different electron delocalization of σ bonds out of the plane of the ring predicted well the discrepancies between NICS(max)σzz and ELFσ. The σ aromatic order of the classic heterobenzenes (C5H5N > C6H6 > C5H5P > C5H5As > C5H5Bi, C5H5Sb) was proved via the level of electronic delocalization.
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publishDate 2014
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spelling curtin-20.500.11937-454182019-02-19T04:25:45Z Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria Hou, B. Yi, P. Wang, Z. Zhang, S. Zhao, J. Mancera, Ricardo Cheng, Y. Zuo, Z. Global Aromaticity s Aromaticity p Aromaticity ELF Heterobenzenes NICS Aromaticity is a key concept in physical organic chemistry. The aromatic order of the classic heterobenzenes was reported in experiment early. However, the unambiguous criteria used to validate the aromaticity of that were controversial or inadequate in theory. In this work, the global aromaticity of the compounds has been studied using the ELF, NICS and ISE. NICS(max)zz was calculated based on the maximum NICS contribution to the out-of-plane zz tensor component. Two types of bonds are observed. The correlations between NICS(max)σzz and NICS(max)πzz with respect to aromaticity are demonstrated, specifically between NICS(max)πzz and ELFπ (cc = 0.98) for π bonds. For σ bonds, the different electron delocalization of σ bonds out of the plane of the ring predicted well the discrepancies between NICS(max)σzz and ELFσ. The σ aromatic order of the classic heterobenzenes (C5H5N > C6H6 > C5H5P > C5H5As > C5H5Bi, C5H5Sb) was proved via the level of electronic delocalization. 2014 Journal Article http://hdl.handle.net/20.500.11937/45418 10.1016/j.comptc.2014.07.012 Elsevier BV fulltext
spellingShingle Global Aromaticity
s Aromaticity
p Aromaticity
ELF
Heterobenzenes
NICS
Hou, B.
Yi, P.
Wang, Z.
Zhang, S.
Zhao, J.
Mancera, Ricardo
Cheng, Y.
Zuo, Z.
Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title_full Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title_fullStr Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title_full_unstemmed Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title_short Assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
title_sort assignment of aromaticity of the classic heterobenzenes by three aromatic criteria
topic Global Aromaticity
s Aromaticity
p Aromaticity
ELF
Heterobenzenes
NICS
url http://hdl.handle.net/20.500.11937/45418