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Thermodynamic and kinetic effects of Lewis acid complexation on a Schiff base present in two tautomeric forms
Author(s) -
Alkorta Ibon,
Elguero José,
Popelier Paul L.A.
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1813
Subject(s) - tautomer , chemistry , pyridine , schiff base , lewis acids and bases , computational chemistry , kinetic energy , ring (chemistry) , density functional theory , pyridoxal , stereochemistry , medicinal chemistry , organic chemistry , catalysis , physics , phosphate , quantum mechanics
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.