Cation-π interactions

A theoretical investigation of the interaction of metallic and organic cations with alkenes, arenes, and heteroarenes

Dongwook Kim, Shaowen Hu, Tarakeshwar Pilarisetty, Kwang S. Kim, James M. Lisy

Research output: Contribution to journalArticle

217 Citations (Scopus)

Abstract

The nature of the cation-π interaction has been examined by carrying out high level ab initio calculations of both metallic (Li+,Na+,K+, and Ag+) and organic (NH4+, C(NH2)3 +, and N(CH3)4 +) cations with different classes of π systems, viz. alkenes (ethene), arenes (benzene), and heteroarenes (pyrrole). The calculations, which include a rigorous decomposition of the interaction energies, indicate that the interaction of these π systems with the metal cations is characterized by contributions from both electrostatic and induction energies, with the contribution of the latter being dominant. Though the contributions of dispersion energies are negligible in the cation-π complexes involving Li+ and Na+, they assume significant proportions in the complexes involving K+ and Ag+. In the π complexes of the organic cations, the repulsive exchange contributions are much larger than the attractive electrostatic contributions in the π complexes of organic cations, and thus, the contributions of both induction and dispersion energies are important. While inclusion of electron correlation is essential in obtaining accurate estimates of the dispersion energy, it also magnifies the contribution of the induction energies in the vt complexes of the organic cations. This results in significant consequences in the evaluation of geometries and energies of these cation-π complexes. The major difference between the cation-π and cation-H2O complexes stems from the differences in the relative contributions of electrostatic and induction energies, a foreknowledge of which is vital in the design of ion-selective ionophores and receptors. The blue shift in the highly IR active out-of-plane CH bending mode of the π systems in these complexes is representative of the strength of the cation-π interaction.

Original languageEnglish (US)
Pages (from-to)1228-1238
Number of pages11
JournalJournal of Physical Chemistry A
Volume107
Issue number8
DOIs
StatePublished - Feb 27 2003
Externally publishedYes

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Alkenes
alkenes
Cations
cations
interactions
induction
Electrostatics
energy
electrostatics
Electron correlations
Pyrroles
Ionophores
pyrroles
Benzene
stems
blue shift
proportion
Metals
benzene
inclusions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Cation-π interactions : A theoretical investigation of the interaction of metallic and organic cations with alkenes, arenes, and heteroarenes. / Kim, Dongwook; Hu, Shaowen; Pilarisetty, Tarakeshwar; Kim, Kwang S.; Lisy, James M.

In: Journal of Physical Chemistry A, Vol. 107, No. 8, 27.02.2003, p. 1228-1238.

Research output: Contribution to journalArticle

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