2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study

Damian Moran, Kengkaj Sukcharoenphon, Ralph Puchta, Henry F. Schaefer, Paul V R Schleyer, Carl Hoff

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Abstract

The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (vS-H stretch) for 2SH was observed in toluene, C6D6, heptane, or methylene chloride solutions. Although, Cs 2SH is 2.61 kcal/mol more stable than Cs 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G-(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C6D6) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS*) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G-(3df,2p) optimized C2 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C2h 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C2 2TS* dimer transition state. Dimerization equilibrium measurements (FTIR, C6D6) over the temperature range 22-63°C agree: Keq298 = 165 ± 40 M-I, ΔH = -7.0 ± 0.7 kcal/mol, and ΔS = -13.4 ± 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 Å above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.

Original languageEnglish
Pages (from-to)9061-9069
Number of pages9
JournalJournal of Organic Chemistry
Volume67
Issue number25
DOIs
StatePublished - Dec 13 2002

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Thiones
Dimers
Fourier transforms
Toluene
Infrared radiation
Thioamides
Heptanes
Dimerization
Methylene Chloride
Chemical shift
Sulfhydryl Compounds
Density functional theory
Hydrogen
Enthalpy
Entropy
Gases
Temperature
Experiments

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study. / Moran, Damian; Sukcharoenphon, Kengkaj; Puchta, Ralph; Schaefer, Henry F.; Schleyer, Paul V R; Hoff, Carl.

In: Journal of Organic Chemistry, Vol. 67, No. 25, 13.12.2002, p. 9061-9069.

Research output: Contribution to journalArticle

Moran, Damian ; Sukcharoenphon, Kengkaj ; Puchta, Ralph ; Schaefer, Henry F. ; Schleyer, Paul V R ; Hoff, Carl. / 2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study. In: Journal of Organic Chemistry. 2002 ; Vol. 67, No. 25. pp. 9061-9069.
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abstract = "The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (vS-H stretch) for 2SH was observed in toluene, C6D6, heptane, or methylene chloride solutions. Although, Cs 2SH is 2.61 kcal/mol more stable than Cs 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G-(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C6D6) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS*) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G-(3df,2p) optimized C2 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C2h 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C2 2TS* dimer transition state. Dimerization equilibrium measurements (FTIR, C6D6) over the temperature range 22-63°C agree: Keq298 = 165 ± 40 M-I, ΔH = -7.0 ± 0.7 kcal/mol, and ΔS = -13.4 ± 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 {\AA} above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.",
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T1 - 2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study

AU - Moran, Damian

AU - Sukcharoenphon, Kengkaj

AU - Puchta, Ralph

AU - Schaefer, Henry F.

AU - Schleyer, Paul V R

AU - Hoff, Carl

PY - 2002/12/13

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N2 - The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (vS-H stretch) for 2SH was observed in toluene, C6D6, heptane, or methylene chloride solutions. Although, Cs 2SH is 2.61 kcal/mol more stable than Cs 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G-(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C6D6) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS*) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G-(3df,2p) optimized C2 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C2h 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C2 2TS* dimer transition state. Dimerization equilibrium measurements (FTIR, C6D6) over the temperature range 22-63°C agree: Keq298 = 165 ± 40 M-I, ΔH = -7.0 ± 0.7 kcal/mol, and ΔS = -13.4 ± 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 Å above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.

AB - The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (vS-H stretch) for 2SH was observed in toluene, C6D6, heptane, or methylene chloride solutions. Although, Cs 2SH is 2.61 kcal/mol more stable than Cs 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G-(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C6D6) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS*) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G-(3df,2p) optimized C2 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C2h 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C2 2TS* dimer transition state. Dimerization equilibrium measurements (FTIR, C6D6) over the temperature range 22-63°C agree: Keq298 = 165 ± 40 M-I, ΔH = -7.0 ± 0.7 kcal/mol, and ΔS = -13.4 ± 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 Å above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.

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