Publication Date:
2014-05-21
Description:
Density functional theory method and B3LYP/6-311++G(d,p) level of theory were used to determine the acidity of alkyl sulfonic acids and polyolalkyl sulfonic acids in the gas and solution (H 2 O, DMSO, and CH 3 CN) phase. Polarized continuum model was applied to calculate p K a values of alkyl sulfonic acids and polyolalkyl sulfonic acids . A comparison between acidity of alkyl sulfonic acids and polyolalkyl sulfonic acids in the gas and solution phase indicates that the acidity strength of polyolalkyl sulfonic acids enhances with the increase of the cooperativity effect of intramolecular hydrogen bonds in polyolalkyl sulfonic acids . Natural bond orbital and quantum theory of atoms in molecules analyses also confirm the role of cooperativity effect on the acidity of polyolalkyl sulfonic acids . Copyright © 2014 John Wiley & Sons, Ltd. • The cooperativity effect of intramolecular hydrogen bonds in polyolalkyl sulfonic acids leads to an increase in the acidity strength in the gas phase and solution (H 2 O, DMSO, and CH 3 CN). • The electron density values for the first hydrogen bond in polyolalkyl sulfonic acids increase by addition of the number of hydroxyl groups. • Quantum theory of atoms in molecules calculations show that the intramolecular hydrogen bonds in polyolalkyl sulfonic acids are electrostatic (closed-shell) interaction in the nature.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
