Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents

J. Bromilow, J. L M Abboud, C. B. Lebrilla, R. W. Taft, G. Scorrano, V. Lucchini

Research output: Contribution to journalArticle

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Abstract

The standard free energies of formation of gaseous complexes between monoprotonic oxonium ions and acetonitrile have been obtained by using the ion cyclotron resonance equilibrium constant method for exchange of acetonitrile between the ions. The results show that the "solvation" by a single molecule of acetonitrile in the gas phase reproduces the important diverse effects of molecular structure on oxonium ion solvation by bulk water. It is estimated from the present results that the effects of solvation by bulk water are only about three times as great as the corresponding effects of "solvation" by a single water molecule in the gas phase. Internal charge delocalization from the protonic site of the oxonium ion strongly reduces solvation. Proton transfer between charge-localized and charge-delocalized oxonium ions may be reversed by differential solvation, both with single H-bonding molecules in the gas phase and with bulk solvent. Further evidence for the site of preferred protonation of esters and amides is provided.

Original languageEnglish (US)
Pages (from-to)5448-5453
Number of pages6
JournalJournal of the American Chemical Society
Volume103
Issue number18
StatePublished - 1981
Externally publishedYes

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Solvation
Acetonitrile
Gases
Ions
Molecules
Water
Cyclotrons
Cyclotron resonance
Proton transfer
Protonation
Equilibrium constants
Molecular Structure
Amides
Molecular structure
Free energy
acetonitrile
hydronium ion
Protons
Ion exchange
Esters

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Bromilow, J., Abboud, J. L. M., Lebrilla, C. B., Taft, R. W., Scorrano, G., & Lucchini, V. (1981). Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents. Journal of the American Chemical Society, 103(18), 5448-5453.

Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents. / Bromilow, J.; Abboud, J. L M; Lebrilla, C. B.; Taft, R. W.; Scorrano, G.; Lucchini, V.

In: Journal of the American Chemical Society, Vol. 103, No. 18, 1981, p. 5448-5453.

Research output: Contribution to journalArticle

Bromilow, J, Abboud, JLM, Lebrilla, CB, Taft, RW, Scorrano, G & Lucchini, V 1981, 'Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents', Journal of the American Chemical Society, vol. 103, no. 18, pp. 5448-5453.
Bromilow J, Abboud JLM, Lebrilla CB, Taft RW, Scorrano G, Lucchini V. Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents. Journal of the American Chemical Society. 1981;103(18):5448-5453.
Bromilow, J. ; Abboud, J. L M ; Lebrilla, C. B. ; Taft, R. W. ; Scorrano, G. ; Lucchini, V. / Oxonium ions. Solvatin by single acetonitrile molecules in the gas phase and by bulk solvents. In: Journal of the American Chemical Society. 1981 ; Vol. 103, No. 18. pp. 5448-5453.
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AU - Bromilow, J.

AU - Abboud, J. L M

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AU - Taft, R. W.

AU - Scorrano, G.

AU - Lucchini, V.

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N2 - The standard free energies of formation of gaseous complexes between monoprotonic oxonium ions and acetonitrile have been obtained by using the ion cyclotron resonance equilibrium constant method for exchange of acetonitrile between the ions. The results show that the "solvation" by a single molecule of acetonitrile in the gas phase reproduces the important diverse effects of molecular structure on oxonium ion solvation by bulk water. It is estimated from the present results that the effects of solvation by bulk water are only about three times as great as the corresponding effects of "solvation" by a single water molecule in the gas phase. Internal charge delocalization from the protonic site of the oxonium ion strongly reduces solvation. Proton transfer between charge-localized and charge-delocalized oxonium ions may be reversed by differential solvation, both with single H-bonding molecules in the gas phase and with bulk solvent. Further evidence for the site of preferred protonation of esters and amides is provided.

AB - The standard free energies of formation of gaseous complexes between monoprotonic oxonium ions and acetonitrile have been obtained by using the ion cyclotron resonance equilibrium constant method for exchange of acetonitrile between the ions. The results show that the "solvation" by a single molecule of acetonitrile in the gas phase reproduces the important diverse effects of molecular structure on oxonium ion solvation by bulk water. It is estimated from the present results that the effects of solvation by bulk water are only about three times as great as the corresponding effects of "solvation" by a single water molecule in the gas phase. Internal charge delocalization from the protonic site of the oxonium ion strongly reduces solvation. Proton transfer between charge-localized and charge-delocalized oxonium ions may be reversed by differential solvation, both with single H-bonding molecules in the gas phase and with bulk solvent. Further evidence for the site of preferred protonation of esters and amides is provided.

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