Group electronegativities from benzene ring deformations: A quantum chemical study

Anna Rita Campanelli, Aldo Domenicano, Fabio Ramondo, I. Hargittai

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

We propose a new scale of group electronegativities, derived from benzene ring deformations in Ph-X molecules. A recent analysis of such deformations (Campanelli, A. R.; Domenicano, A.; Ramondo, F. J. Phys. Chem. A 2003, 107, 6429) has shown that two orthogonal linear combinations of the internal ring angles, termed SE and SR, are directly related to the electronegativity and resonance effects of the substituent, respectively. In the present paper, we show that SE increases linearly with the electronegativity of X within each of the first two rows of the periodic table, acting as a sensitive indicator of the polarity of the Ph-X bond. By using SE values from ab initio quantum chemical calculations, we have derived the electronegativities of 100 organic and inorganic groups. Nonbonded interactions with the ortho hydrogens and carbons may fictitiously alter the electronegativity of a group; in most cases, however, they are easily eluded by changing the conformation of the substituent with respect to the benzene ring. Although the atom directly linked to the ring tends to dominate the electronegativity of a group, the role of its adjacent atoms is also important. Their effect depends markedly on the nature of chemical bonding and electron density distribution within the group.

Original languageEnglish
Pages (from-to)4940-4948
Number of pages9
JournalJournal of Physical Chemistry A
Volume108
Issue number22
DOIs
Publication statusPublished - Jun 3 2004

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Electronegativity
Benzene
benzene
rings
ortho hydrogen
Atoms
Electronic density of states
atoms
density distribution
polarity
Conformations
Hydrogen
Carbon
carbon
Molecules
molecules
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Group electronegativities from benzene ring deformations : A quantum chemical study. / Campanelli, Anna Rita; Domenicano, Aldo; Ramondo, Fabio; Hargittai, I.

In: Journal of Physical Chemistry A, Vol. 108, No. 22, 03.06.2004, p. 4940-4948.

Research output: Contribution to journalArticle

Campanelli, Anna Rita ; Domenicano, Aldo ; Ramondo, Fabio ; Hargittai, I. / Group electronegativities from benzene ring deformations : A quantum chemical study. In: Journal of Physical Chemistry A. 2004 ; Vol. 108, No. 22. pp. 4940-4948.
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