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Relation between resonance energy and substituent resonance effect in P ‐phenols
Author(s) -
Krygowski Tadeusz M.,
Stępień Beata T.,
Cyrański Michal K.,
Ejsmont Krzysztof
Publication year - 2005
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.960
Subject(s) - substituent , chemistry , aromaticity , delocalized electron , phenol , resonance (particle physics) , electron delocalization , computational chemistry , chemical shift , phenols , stereochemistry , molecule , organic chemistry , atomic physics , physics
Molecular geometries of phenol and its 17 p ‐substituted derivatives were optimized at the B3LYP/6–311 + G** level of theory. Three homodesmotic and three isodesmotic reaction schemes were used to estimate aromatic stabilization energies (ASE) and the substituent effect stabilization energy (SESE). Other descriptors of π‐electron delocalization (HOMA and NICS, NICS(1) and NICS(1) zz ) were also estimated. The SESE and ASE values correlated well with one another as well as with substituent constants. Much worse correlations with substituent constants were found for other aromaticity indices. The NICS(1) zz values are the most negative for unsubstituted phenol, indicating its highest aromaticity; that was not the case for NICS(1) and NICS. Copyright © 2005 John Wiley & Sons, Ltd.