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Hydroxyl stretching in substituted phenols: An AM1 study
Author(s) -
Brewster Marcus E.,
Huang MingJu,
Pop Emil,
Bodor Nicholas
Publication year - 1993
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560480705
Subject(s) - chemistry , phenols , steric effects , phenol , valence (chemistry) , gas phase , computational chemistry , electronic correlation , molecular orbital , phase (matter) , molecule , organic chemistry
Hydroxyl‐stretching frequencies ( v OH ) were estimated for a number of 4‐substituted and 2,6‐disubstituted phenols using the AM1 all‐valence electron molecular orbital approximation. There was significant correlation between calculated and experimentally observed frequencies with better correlation observed with the gas phase as compared with dilute solution‐phase values. Significant Hammett sigma–rho relationships were recorded for the 4‐substituted phenols, consistent with experimental observations. The v OH stretching frequency associated with the equilibrium structure of 2,6‐di‐ t ‐butylphenol was calculated to be 15 cm −1 higher than that of phenol and this increase was attributed to steric interactions that act to effectively shorten the OH bond length. © 1993 John Wiley & Sons, Inc.