Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms

Ibon Alkorta; José Elguero; Paul L A Popelier

doi:10.1002/poc.1813

Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms

Ibon Alkorta, José Elguero, Paul L A Popelier

Research output: Contribution to journal › Article › peer-review

Abstract

The effect of complexation with Lewis acids on the tautomeric equilibrium of a derivative of pyridoxal has been explored using density functional theory. Three complexation sites (pyridine nitrogen, aromatic ring, and carbonyl group) have been considered. The tautomeric equilibrium can be modulated with the formation of complexes at the different sites. The changes observed in the geometric, energetic and electronic properties of the tautomers and transition states have been analyzed. Relationships have been found between those parameters, including a relationship between energetic and geometric parameters in agreement with the Hammond postulate. Copyright © 2010 John Wiley & Sons, Ltd.

Original language	English
Pages (from-to)	744-750
Number of pages	6
Journal	Journal of Physical Organic Chemistry
Volume	24
Issue number	9
DOIs	https://doi.org/10.1002/poc.1813
Publication status	Published - Sept 2011

Keywords

AIM
allosteric
B3LYP
DFT
pyridoxal

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10.1002/poc.1813

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title = "Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms",

abstract = "The effect of complexation with Lewis acids on the tautomeric equilibrium of a derivative of pyridoxal has been explored using density functional theory. Three complexation sites (pyridine nitrogen, aromatic ring, and carbonyl group) have been considered. The tautomeric equilibrium can be modulated with the formation of complexes at the different sites. The changes observed in the geometric, energetic and electronic properties of the tautomers and transition states have been analyzed. Relationships have been found between those parameters, including a relationship between energetic and geometric parameters in agreement with the Hammond postulate. Copyright {\textcopyright} 2010 John Wiley & Sons, Ltd.",

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author = "Ibon Alkorta and Jos{\'e} Elguero and Popelier, {Paul L A}",

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journal = "Journal of Physical Organic Chemistry",

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publisher = "John Wiley & Sons Ltd",

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T1 - Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms

AU - Alkorta, Ibon

AU - Elguero, José

AU - Popelier, Paul L A

PY - 2011/9

Y1 - 2011/9

N2 - The effect of complexation with Lewis acids on the tautomeric equilibrium of a derivative of pyridoxal has been explored using density functional theory. Three complexation sites (pyridine nitrogen, aromatic ring, and carbonyl group) have been considered. The tautomeric equilibrium can be modulated with the formation of complexes at the different sites. The changes observed in the geometric, energetic and electronic properties of the tautomers and transition states have been analyzed. Relationships have been found between those parameters, including a relationship between energetic and geometric parameters in agreement with the Hammond postulate. Copyright © 2010 John Wiley & Sons, Ltd.

AB - The effect of complexation with Lewis acids on the tautomeric equilibrium of a derivative of pyridoxal has been explored using density functional theory. Three complexation sites (pyridine nitrogen, aromatic ring, and carbonyl group) have been considered. The tautomeric equilibrium can be modulated with the formation of complexes at the different sites. The changes observed in the geometric, energetic and electronic properties of the tautomers and transition states have been analyzed. Relationships have been found between those parameters, including a relationship between energetic and geometric parameters in agreement with the Hammond postulate. Copyright © 2010 John Wiley & Sons, Ltd.

KW - AIM

KW - allosteric

KW - B3LYP

KW - DFT

KW - pyridoxal

U2 - 10.1002/poc.1813

DO - 10.1002/poc.1813

M3 - Article

SN - 0894-3230

VL - 24

SP - 744

EP - 750

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

IS - 9

ER -

Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms

Abstract

Keywords

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