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Molecular basis of LFER: theoretical study of polar substituent effect in aliphatic series |
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| Authors: | Robert Ponec Sofie Van Damme |
| Institution: | 1. Institute of Chemical Process Fundamentals, Czech Academy of Sciences, 165 02 Prague 6, Suchdol 2, Czech RepublicInstitute of Chemical Process Fundamentals, Czech Academy of Sciences, 165 02 Prague 6, Suchdol 2, Czech Republic.===;2. Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281, B‐9000, Belgium |
| Abstract: | The nature of inductive substituent effect on the gas phase acidity of several series of aliphatic carboxylic acids with rigid molecular skeletons was analyzed using the recently proposed quantum chemical approach based on the theory of proton affinity proposed by Longuet‐Higgins. The results of the analysis suggest that the substituent induced variation of the acidity is in all series due to electrostatic field‐effect which in the gas phase can reasonably be characterized by Kirkwood–Westheimer theory. Copyright © 2007 John Wiley & Sons, Ltd. |
| Keywords: | nature of inductive effect field‐effect |