Premium
Relationship between substituent effect and aromaticity – Part III: naphthalene as a transmitting moiety for substituent effect
Author(s) -
Krygowski Tadeusz M.,
Palusiak Marcin,
Płonka Anna,
ZacharaHoreglad Joanna E.
Publication year - 2007
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.1127
Subject(s) - chemistry , substituent , aromaticity , moiety , intramolecular force , naphthalene , ion , computational chemistry , crystallography , stereochemistry , molecule , organic chemistry
Molecular geometry of 10 isomeric nitronaphtholate ions (excluding peri ‐ and ortho ‐type substituted systems), 1‐ and 2‐naphtholate ions, 1‐ and 2‐nitronaphthalene, meta ‐ and para ‐nitrophenolate, phenolate, and nitrobenzene were optimized at B3LYP/6‐311G** level of approximation. Substituent effect stabilization energy (SESE), geometry‐based aromaticity index HOMA, magnetism‐based indices NICS, NICS(1), NICS(1) zz , and parameters characterizing Bond Critical Points (BCP) ( ρ , ▿ 2 ρ , ellipticity, ion/cov) of the Bader AIM theory were used to characterize transmitting properties for substituent effect through the naphthalene moiety. It results from our study that the studied systems could be clearly divided into two groups, (i) a para ‐type group, where the intramolecular charge transfer between the π ‐electron donating and π ‐electron accepting substituents can be described by canonical forms with charge separation (as in the case of para ‐nitrophenolate) and (ii) a meta ‐type group, where this transfer requires using canonical forms with double charge separation (as in the case of meta ‐nitrophenolate). Copyright © 2007 John Wiley & Sons, Ltd.