Matrix-isolation FT-IR studies and ab initio calculations of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 6. Experimental observation of a water-induced tautomeric shift for 2-hydroxypyrimidine and 5-bromo-2-hydroxypyrimidine

Johan Smets, Alain Destexhe, Ludwik Adamowicz, Guido Maes

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Abstract

The H-bond interaction of the cytosine model compound 2-hydroxypyrimidine and its 5-bromo derivative with water is investigated using the combined matrix-isolation FT-IR and theoretical ab initio method. As predicted by the ab initio calculations, both compounds occur dominantly in the hydroxy tautomeric forms. The estimated KT(h/o) values are 60 and 184, respectively. When water is added to the Ar matrix, a noticeable shift of the tautomeric equilibrium towards the oxo form is observed. The theoretical results indicate that the closed N⋯H-O(H)⋯H-O and C=O⋯H-O(H)⋯H-N H-bonded water complexes are the most stable systems for the hydroxy and the oxo tautomers, respectively. The experimental spectra are consistent with this prediction, but additional structures, such as an open N⋯H-OH complex of the hydroxy tautomer, are also identified. The frequency shift of the stretching mode of doubly H-bonded water in the two closed complexes is larger, and the ratio between the calculated and measured frequencies smaller than expected from the correlation established before for open, singly H-bonded complexes involving similar molecules. Although some cooperativity exists between the two H bonds in each of the closed complexes, this effect is limited because the geometrical structures of both H bonds are noticeably perturbed from the perfect alignment due to the cyclic arrangement of the complex. A possible mechanism of the proton transfer process leading from the hydroxy to the oxo tautomeric form is discussed in terms of proton tunneling and in relation to recent literature data.

Original languageEnglish (US)
Pages (from-to)8157-8168
Number of pages12
JournalJournal of Physical Chemistry A
Volume102
Issue number42
StatePublished - Oct 15 1998

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Cytosine
tautomers
Hydrogen
isolation
Molecules
Water
shift
hydrogen
matrices
water
molecules
Proton transfer
protons
frequency shift
Stretching
Protons
alignment
Derivatives
2-hydroxypyrimidine
isocytosine

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Matrix-isolation FT-IR studies and ab initio calculations of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 6. Experimental observation of a water-induced tautomeric shift for 2-hydroxypyrimidine and 5-bromo-2-hydroxypyrimidine",
abstract = "The H-bond interaction of the cytosine model compound 2-hydroxypyrimidine and its 5-bromo derivative with water is investigated using the combined matrix-isolation FT-IR and theoretical ab initio method. As predicted by the ab initio calculations, both compounds occur dominantly in the hydroxy tautomeric forms. The estimated KT(h/o) values are 60 and 184, respectively. When water is added to the Ar matrix, a noticeable shift of the tautomeric equilibrium towards the oxo form is observed. The theoretical results indicate that the closed N⋯H-O(H)⋯H-O and C=O⋯H-O(H)⋯H-N H-bonded water complexes are the most stable systems for the hydroxy and the oxo tautomers, respectively. The experimental spectra are consistent with this prediction, but additional structures, such as an open N⋯H-OH complex of the hydroxy tautomer, are also identified. The frequency shift of the stretching mode of doubly H-bonded water in the two closed complexes is larger, and the ratio between the calculated and measured frequencies smaller than expected from the correlation established before for open, singly H-bonded complexes involving similar molecules. Although some cooperativity exists between the two H bonds in each of the closed complexes, this effect is limited because the geometrical structures of both H bonds are noticeably perturbed from the perfect alignment due to the cyclic arrangement of the complex. A possible mechanism of the proton transfer process leading from the hydroxy to the oxo tautomeric form is discussed in terms of proton tunneling and in relation to recent literature data.",
author = "Johan Smets and Alain Destexhe and Ludwik Adamowicz and Guido Maes",
year = "1998",
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language = "English (US)",
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pages = "8157--8168",
journal = "Journal of Physical Chemistry A",
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T1 - Matrix-isolation FT-IR studies and ab initio calculations of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 6. Experimental observation of a water-induced tautomeric shift for 2-hydroxypyrimidine and 5-bromo-2-hydroxypyrimidine

AU - Smets, Johan

AU - Destexhe, Alain

AU - Adamowicz, Ludwik

AU - Maes, Guido

PY - 1998/10/15

Y1 - 1998/10/15

N2 - The H-bond interaction of the cytosine model compound 2-hydroxypyrimidine and its 5-bromo derivative with water is investigated using the combined matrix-isolation FT-IR and theoretical ab initio method. As predicted by the ab initio calculations, both compounds occur dominantly in the hydroxy tautomeric forms. The estimated KT(h/o) values are 60 and 184, respectively. When water is added to the Ar matrix, a noticeable shift of the tautomeric equilibrium towards the oxo form is observed. The theoretical results indicate that the closed N⋯H-O(H)⋯H-O and C=O⋯H-O(H)⋯H-N H-bonded water complexes are the most stable systems for the hydroxy and the oxo tautomers, respectively. The experimental spectra are consistent with this prediction, but additional structures, such as an open N⋯H-OH complex of the hydroxy tautomer, are also identified. The frequency shift of the stretching mode of doubly H-bonded water in the two closed complexes is larger, and the ratio between the calculated and measured frequencies smaller than expected from the correlation established before for open, singly H-bonded complexes involving similar molecules. Although some cooperativity exists between the two H bonds in each of the closed complexes, this effect is limited because the geometrical structures of both H bonds are noticeably perturbed from the perfect alignment due to the cyclic arrangement of the complex. A possible mechanism of the proton transfer process leading from the hydroxy to the oxo tautomeric form is discussed in terms of proton tunneling and in relation to recent literature data.

AB - The H-bond interaction of the cytosine model compound 2-hydroxypyrimidine and its 5-bromo derivative with water is investigated using the combined matrix-isolation FT-IR and theoretical ab initio method. As predicted by the ab initio calculations, both compounds occur dominantly in the hydroxy tautomeric forms. The estimated KT(h/o) values are 60 and 184, respectively. When water is added to the Ar matrix, a noticeable shift of the tautomeric equilibrium towards the oxo form is observed. The theoretical results indicate that the closed N⋯H-O(H)⋯H-O and C=O⋯H-O(H)⋯H-N H-bonded water complexes are the most stable systems for the hydroxy and the oxo tautomers, respectively. The experimental spectra are consistent with this prediction, but additional structures, such as an open N⋯H-OH complex of the hydroxy tautomer, are also identified. The frequency shift of the stretching mode of doubly H-bonded water in the two closed complexes is larger, and the ratio between the calculated and measured frequencies smaller than expected from the correlation established before for open, singly H-bonded complexes involving similar molecules. Although some cooperativity exists between the two H bonds in each of the closed complexes, this effect is limited because the geometrical structures of both H bonds are noticeably perturbed from the perfect alignment due to the cyclic arrangement of the complex. A possible mechanism of the proton transfer process leading from the hydroxy to the oxo tautomeric form is discussed in terms of proton tunneling and in relation to recent literature data.

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