A quantitative scale for the degree of aromaticity and antiaromaticity: A comparison of theoretical and experimental enthalpies of hydrogenation

Zoltán Mucsi, B. Viskolcz, I. Csizmadia

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34 Citations (Scopus)

Abstract

Chemical structures and transition states are often influenced by aromatic stabilization or antiaromatic destabilizing effects, which are not easy to characterize theoretically. The exact description and precise quantification of the aromatic characteristics of ring structures is difficult and requires special theoretical investigation. The present paper suggests a novel, yet simple, method to quantify both aromatic and antiaromatic qualities on the same linear scale, by using the experimentally measured or theoretically computed enthalpy of hydrogenation reaction of the compound examined [ΔH 2(examined)]. A reference hydrogenation reaction is also considered on a corresponding nonaromatic reference compound [ΔH 2(reference)] to cancel all secondary structure destabilization factors, such as ring strain or double bond strain. From these data the relative enthalpy of hydrogenation may easily be calculated: ΔΔH H2 = ΔHH2(examined) - ΔH H2(reference). In the present work concept, the ΔΔH H2 value of benzene defines the completely aromatic character (+100%), and the closed shell of the singlet cyclobutadiene represents maximum antiaromaticity (-100%). The component ΔHH2 values were computed at different levels of theory offering a computational "method-independent" measure for aromaticity. A total of 28 well-known aromatic, antiaromatic and nonaromatic, neutral and charged compounds were examined to demonstrate the efficiency of this methodology. Finally, a correlation was made between the calculated aromaticity percentage of the compound examined and their popular Schleyers NICS values.

Original languageEnglish
Pages (from-to)1123-1132
Number of pages10
JournalJournal of Physical Chemistry A
Volume111
Issue number6
DOIs
Publication statusPublished - Feb 15 2007

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Hydrogenation
hydrogenation
Enthalpy
enthalpy
Computational methods
Benzene
ring structures
destabilization
Stabilization
stabilization
benzene
methodology
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "A quantitative scale for the degree of aromaticity and antiaromaticity: A comparison of theoretical and experimental enthalpies of hydrogenation",
abstract = "Chemical structures and transition states are often influenced by aromatic stabilization or antiaromatic destabilizing effects, which are not easy to characterize theoretically. The exact description and precise quantification of the aromatic characteristics of ring structures is difficult and requires special theoretical investigation. The present paper suggests a novel, yet simple, method to quantify both aromatic and antiaromatic qualities on the same linear scale, by using the experimentally measured or theoretically computed enthalpy of hydrogenation reaction of the compound examined [ΔH 2(examined)]. A reference hydrogenation reaction is also considered on a corresponding nonaromatic reference compound [ΔH 2(reference)] to cancel all secondary structure destabilization factors, such as ring strain or double bond strain. From these data the relative enthalpy of hydrogenation may easily be calculated: ΔΔH H2 = ΔHH2(examined) - ΔH H2(reference). In the present work concept, the ΔΔH H2 value of benzene defines the completely aromatic character (+100{\%}), and the closed shell of the singlet cyclobutadiene represents maximum antiaromaticity (-100{\%}). The component ΔHH2 values were computed at different levels of theory offering a computational {"}method-independent{"} measure for aromaticity. A total of 28 well-known aromatic, antiaromatic and nonaromatic, neutral and charged compounds were examined to demonstrate the efficiency of this methodology. Finally, a correlation was made between the calculated aromaticity percentage of the compound examined and their popular Schleyers NICS values.",
author = "Zolt{\'a}n Mucsi and B. Viskolcz and I. Csizmadia",
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AU - Viskolcz, B.

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AB - Chemical structures and transition states are often influenced by aromatic stabilization or antiaromatic destabilizing effects, which are not easy to characterize theoretically. The exact description and precise quantification of the aromatic characteristics of ring structures is difficult and requires special theoretical investigation. The present paper suggests a novel, yet simple, method to quantify both aromatic and antiaromatic qualities on the same linear scale, by using the experimentally measured or theoretically computed enthalpy of hydrogenation reaction of the compound examined [ΔH 2(examined)]. A reference hydrogenation reaction is also considered on a corresponding nonaromatic reference compound [ΔH 2(reference)] to cancel all secondary structure destabilization factors, such as ring strain or double bond strain. From these data the relative enthalpy of hydrogenation may easily be calculated: ΔΔH H2 = ΔHH2(examined) - ΔH H2(reference). In the present work concept, the ΔΔH H2 value of benzene defines the completely aromatic character (+100%), and the closed shell of the singlet cyclobutadiene represents maximum antiaromaticity (-100%). The component ΔHH2 values were computed at different levels of theory offering a computational "method-independent" measure for aromaticity. A total of 28 well-known aromatic, antiaromatic and nonaromatic, neutral and charged compounds were examined to demonstrate the efficiency of this methodology. Finally, a correlation was made between the calculated aromaticity percentage of the compound examined and their popular Schleyers NICS values.

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