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Estimation of Hammett sigma constants from calculated atomic charges using partial least squares regression
Author(s) -
Genix Pierre,
Jullien Hervé,
Le Goas Rémi
Publication year - 1996
Publication title -
journal of chemometrics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.47
H-Index - 92
eISSN - 1099-128X
pISSN - 0886-9383
DOI - 10.1002/(sici)1099-128x(199609)10:5/6<631::aid-cem451>3.0.co;2-z
Subject(s) - substituent , chemistry , hammett equation , partial least squares regression , computational chemistry , taft equation , molecular orbital , moiety , benzoic acid , stereochemistry , mathematics , organic chemistry , reaction rate constant , quantum mechanics , statistics , molecule , physics , kinetics
Hammett constants describe the electronic donating or withdrawing capabilities of a given substituent. Since Hammett constants represent information of an electronic nature, their values are to be linked with atomic charges and orbital‐derived parameters of the atoms of the substrate bearing the substituent. A series of 132 para‐ and meta‐substituted benzoic acid structures has been built and energy minimized using MOPAC/AM1. Atomic charges and frontier orbital coefficients of the benzoic moiety have been calculated. These parameters were highly interrelated. Using partial least squares regression, we showed that Hammett constants can be satisfactorily estimated from these electronic parameters. © 1996 by John Wiley & Sons, Ltd.