Density functional theory and ab-initio computational study of the 2-hydroxypyridine/2-pyridone system: a comparison with FT-IR data from matrix isolation experiments

Dkhissi, Ahmed; Houben, Linda; Smets, Johan; Adamowicz, Ludwik; Maes, Guido

doi:10.1016/s0022-2860(98)00910-7

Cited by 63 publications

(82 citation statements)

References 35 publications

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“…In this respect, it is quite interesting to investigate the tautomerization of PY to HY by using molecular clusters as a microscopic model for the environment. Most ab initio calculations 28,[30][31][32][33][34] to date have focused on the hydrogen-bonding interactions between the two tautomers and the water molecule or the spectra studies of them; only a few studies 23, 24,29 have attempted to examine the proton-transfer mechanism of PY to HY. Field and Hiller 23 have used the 3-21G basis incorporating the CI expansion to investigate the proton-transfer mechanism of PY to HY.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

et al. 2005

J. Phys. Chem. A

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The proton-transfer mechanism in the isolated, mono, dehydrated forms and dimers of 2-pyridone and the effect of hydration or self-assistance on the transition state structures corresponding to proton transfer from the keto form to the enol form have been investigated using B3LYP and BH-LYP hybrid density functional methods at the 6-311++G (2d, 2p) basis set level. The barrier heights for both H2O-assisted and self-assisted reactions are significantly lower than that of the bare tautomerization reaction from 2-pyridone to 2-hydroxypyridine, implying the importance of the superior catalytic effect of H2O and (H2O)2 and the important role of 2-pyridone itself for the intramolecular proton transfer. Long-range solvent effects have also been taken into account by using the continuum model (Onsager model and polarizable continuum model (PCM)) of water. The tautomerization energies and the potential energy barriers are increased both for the water-assisted and for the self-assisted reaction because of the bulk solvent, which imply that the tautomerization of PY becomes less favorable in the polar solvent.

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Section: Introductionmentioning

confidence: 99%

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

et al. 2005

J. Phys. Chem. A

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“…Spectroscopic data indicates that the hydroxy form is the major tautomer in the gas phase. [30][31][32] In the solid state, however, the formation of hydrogen bonded dimers seems to favour the 2-pyridone tautomers. [33] Similarly, we found, by 1 H and 13 C NMR spectroscopy in acetone, that 2-hydroxypyridine and 2-pyridinethiol exist exclusively as the 2-pyridone and 2-pyridinethione tautomers, respectively.…”

Section: Resultsmentioning

confidence: 99%

Platinum(II) Alkynyl Complexes Containing N‐ and S‐Propargylated Ligands: Synthesis, Structures and Formation of Pt^II/Ag^I Coordination Compounds

2007

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Alkylation of 2-hydroxypyridine, 2-pyridinethiol, 2-hydroxy-4-methylquinoline, phthalimide and pyrazole with propargyl bromide gave a series of alkynes in high yield. These alkynes were reacted with the chloroplatinum(II) compounds trans-[PtCl 2 (PPh 3 ) 2 ] and cis-[PtCl 2 (dppe)] to afford the respective trans-and cis-bis(alkynyl)platinum(II) complexes, which were characterised by spectroscopic analysis and by X-ray

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“…It tautomerizes to form 2-pyridone (2-PY) by a proton transfer between the nitrogen and oxygen atoms [1]. The tautomerism between 2-hydroxypyridine and 2-pyridone has been confirmed by X-ray [2], IR [3,4,5], UV [6], and microwave spectroscopy [7], together with some theoretical studies [8,9,10]. 2-Pyridones play important roles in bioactive systems and in current medicinal chemistry.…”

Section: Introductionmentioning

confidence: 99%

The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit

Hejazi

Osman

Al‐Youbi

et al. 2016

IJMS

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The gas-phase thermal tautomerization reaction between 2-hydroxypyridine (2-HPY) and 2-pyridone (2-PY) was investigated by applying 6-311++G** and aug-cc-pvdz basis sets incorporated into some density functional theory (DFT) and coupled cluster with singles and doubles (CCSD) methods. The geometrical structures, dipole moments, HOMO-LUMO energy gaps, total hyperpolarizability, kinetics and thermodynamics functions were monitored against the effects of the corrections imposed on these functionals. The small experimental energy difference between the two tautomers of 3.23 kJ/mol; was a real test of the accuracy of the applied levels of theory. M062X and CCSD methods predicted the preference of 2-HPY over 2-PY by 5–9 kJ/mol; while B3LYP functional favoured 2-PY by 1–3 kJ/mol. The CAM-B3LYP and ωB97XD functionals yielded mixed results depending on the basis set used. The source of preference of 2-HPY is the minimal steric hindrance and electrostatic repulsion that subdued the huge hyperconjugation in 2-PY. A 1,3-proton shift intramolecular gas-phase tautomerization yielded a high average activation of 137.152 kJ/mol; while the intermolecular mixed dimer interconversion gave an average barrier height of 30.844 kJ/mol. These findings are boosted by a natural bond orbital (NBO) technique. The low total hyperpolarizabilities of both tautomers mark out their poor nonlinear optical (NLO) behaviour. The enhancement of the total hyperpolarizability of 2-HPY over that of 2-PY is interpreted by the bond length alternation.

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Density functional theory and ab-initio computational study of the 2-hydroxypyridine/2-pyridone system: a comparison with FT-IR data from matrix isolation experiments

Cited by 63 publications

References 35 publications

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

Platinum(II) Alkynyl Complexes Containing N‐ and S‐Propargylated Ligands: Synthesis, Structures and Formation of Pt^II/Ag^I Coordination Compounds

The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit

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Density functional theory and ab-initio computational study of the 2-hydroxypyridine/2-pyridone system: a comparison with FT-IR data from matrix isolation experiments

Cited by 63 publications

References 35 publications

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

Density Functional Study on the Reaction Mechanism of Proton Transfer in 2-Pyridone: Effect of Hydration and Self-Association

Platinum(II) Alkynyl Complexes Containing N‐ and S‐Propargylated Ligands: Synthesis, Structures and Formation of PtII/AgI Coordination Compounds

The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit

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Platinum(II) Alkynyl Complexes Containing N‐ and S‐Propargylated Ligands: Synthesis, Structures and Formation of Pt^II/Ag^I Coordination Compounds