Theoretical and matrix-isolation experimental study on 2(1H)-pyridinethione/2-pyridinethiol

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

Research output: Contribution to journalArticle

70 Citations (Scopus)

Abstract

Tautomerism and infrared spectra of 2(1H)-pyridinethione were studied with theoretical and experimental methods. The relative stabilization energy of thiol and thione tautomers was calculated by using the SCF + MBPT(2) method of quantum chemistry with DZP basis set. The thiol form was predicted to be predominant in the gas phase. Vibrational frequencies and intensities of the IR bands were calculated at the SCF 3-21G* level. In reported experimental IR spectroscopic studies of Ar and N2 matrix-isolated compounds, the thiol and thione tautomers were found in relative concentrations of about 30:1. The phototautomeric reaction - the conversion of the thione form into the thiol form after UV-vis irradiation of the matrix - was observed and used to separate the spectra of the two forms. Comparison of the experimental IR spectra of matrix-isolated and crystalline compounds with the spectra predicted theoretically gave an assignment for the majority of the absorption bands in the spectra of both tautomers.

Original languageEnglish (US)
Pages (from-to)7406-7414
Number of pages9
JournalJournal of Physical Chemistry
Volume94
Issue number19
StatePublished - 1990

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Quantum chemistry
Vibrational spectra
Thiones
Sulfhydryl Compounds
Absorption spectra
isolation
thiols
Stabilization
Irradiation
Crystalline materials
Infrared radiation
tautomers
matrices
Gases
self consistent fields
quantum chemistry
infrared spectra
stabilization
vapor phases
absorption spectra

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical and matrix-isolation experimental study on 2(1H)-pyridinethione/2-pyridinethiol. / Nowak, Maciej J.; Lapinski, Leszek; Rostkowska, Hanna; Leś, Andrzej; Adamowicz, Ludwik.

In: Journal of Physical Chemistry, Vol. 94, No. 19, 1990, p. 7406-7414.

Research output: Contribution to journalArticle

Nowak, MJ, Lapinski, L, Rostkowska, H, Leś, A & Adamowicz, L 1990, 'Theoretical and matrix-isolation experimental study on 2(1H)-pyridinethione/2-pyridinethiol', Journal of Physical Chemistry, vol. 94, no. 19, pp. 7406-7414.
Nowak, Maciej J. ; Lapinski, Leszek ; Rostkowska, Hanna ; Leś, Andrzej ; Adamowicz, Ludwik. / Theoretical and matrix-isolation experimental study on 2(1H)-pyridinethione/2-pyridinethiol. In: Journal of Physical Chemistry. 1990 ; Vol. 94, No. 19. pp. 7406-7414.
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AU - Adamowicz, Ludwik

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