A Theoretical Investigation of Benzene-AlX3 and Ethene-AlX3 (X = H, F, Cl) Interactions

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Abstract

The present report details the results of a high-level theoretical investigation of benzene-AlX3 and ethene-AlX3 (X = H, F, Cl) interactions. The binding energies, preferred modes of interaction of AlX3 with benzene and ethene, and vibrational frequencies for these complexes have been evaluated at the MP2 level using basis sets ranging from the 6-31+G* to the much larger (6-311++G(2df,p) + diffuse(d,p)). In the lowest energy conformers of the benzene complexes, the Al atom is directly placed over one of the benzene carbons, while in the ethene complexes, the Al atom lies above the center of the π bond. The binding energies of both the benzene and ethene complexes of AlX3 are dominated by electrostatic contributions, which is in contrast to the dominance of the electron correlation energy in the benzene-BX3 complexes. A very sharp increase in the negative charge of the benzene carbon closest to the Al atom in the lowest energy conformers of the benzene complexes from -0.2 to -0.4 au points to an important role of activation of the aromatic ring by the Lewis acid in electrophilic aromatic substitution reactions.

Original languageEnglish (US)
Pages (from-to)9116-9124
Number of pages9
JournalJournal of Physical Chemistry A
Volume103
Issue number45
StatePublished - Nov 11 1999
Externally publishedYes

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Benzene
benzene
interactions
Binding energy
Atoms
Carbon
binding energy
atoms
Electron correlations
Lewis Acids
ethylene
carbon
Vibrational spectra
energy
Electrostatics
Substitution reactions
Chemical activation
activation
substitutes
electrostatics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A Theoretical Investigation of Benzene-AlX3 and Ethene-AlX3 (X = H, F, Cl) Interactions. / Pilarisetty, Tarakeshwar; Kim, Kwang S.

In: Journal of Physical Chemistry A, Vol. 103, No. 45, 11.11.1999, p. 9116-9124.

Research output: Contribution to journalArticle

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AB - The present report details the results of a high-level theoretical investigation of benzene-AlX3 and ethene-AlX3 (X = H, F, Cl) interactions. The binding energies, preferred modes of interaction of AlX3 with benzene and ethene, and vibrational frequencies for these complexes have been evaluated at the MP2 level using basis sets ranging from the 6-31+G* to the much larger (6-311++G(2df,p) + diffuse(d,p)). In the lowest energy conformers of the benzene complexes, the Al atom is directly placed over one of the benzene carbons, while in the ethene complexes, the Al atom lies above the center of the π bond. The binding energies of both the benzene and ethene complexes of AlX3 are dominated by electrostatic contributions, which is in contrast to the dominance of the electron correlation energy in the benzene-BX3 complexes. A very sharp increase in the negative charge of the benzene carbon closest to the Al atom in the lowest energy conformers of the benzene complexes from -0.2 to -0.4 au points to an important role of activation of the aromatic ring by the Lewis acid in electrophilic aromatic substitution reactions.

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