Concerted biprotonic tautomerism of 2-hydroxypyridine

Andrzej Leś, Ludwik Adamowicz, Maciej J. Nowak, Leszek Lapinski

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Theoretical ab initio calculations have been performed to estimate the potential energy barrier for a concerted biprotonic tautomerization in 2-hydroxypyridine cyclic dimers. At the SCF/(mixed basis set) level these calculations suggest that this barrier is about 60 kJ mol-1 . This value is about three times smaller than the potential energy barrier for a single proton transfer in monomers. The rate constants for the tautomeric form change in dimers have also been calculated based on the Rice- Ramsperger-Kassel-Marcus theory. The numerical solution of the corresponding kinetic equations (with estimated rate constants) suggests that the concerted biprotonic tautomerization of 2-hydroxypyridine gaseous samples may occur within 4 × 10-5 to 4 × 10-6 s. That should be fast enough to facilitate the tautomeric equilibrium to be achieved in the course of the flight of molecules during deposition of low-temperature matrices. Tautomeric processes involving concerted transfer of two protons in the 2-hydroxypyridine cyclic dimers bonded by two hydrogen bonds seem to provide the most important way of reaching the tautomeric equilibria observed in the gas-phase and matrix-isolation experiments.

Original languageEnglish (US)
Pages (from-to)157-166
Number of pages10
JournalJournal of Molecular Structure: THEOCHEM
Volume312
Issue number2
DOIs
StatePublished - 1994

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Dimers
Energy barriers
dimers
Potential energy
Protons
Rate constants
potential energy
Proton transfer
protons
rice
matrices
kinetic equations
self consistent fields
Hydrogen
isolation
Hydrogen bonds
monomers
Monomers
Gases
flight

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Concerted biprotonic tautomerism of 2-hydroxypyridine. / Leś, Andrzej; Adamowicz, Ludwik; Nowak, Maciej J.; Lapinski, Leszek.

In: Journal of Molecular Structure: THEOCHEM, Vol. 312, No. 2, 1994, p. 157-166.

Research output: Contribution to journalArticle

Leś, Andrzej ; Adamowicz, Ludwik ; Nowak, Maciej J. ; Lapinski, Leszek. / Concerted biprotonic tautomerism of 2-hydroxypyridine. In: Journal of Molecular Structure: THEOCHEM. 1994 ; Vol. 312, No. 2. pp. 157-166.
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