TY - JOUR
T1 - Substituent Effects of -NO and -NO2 Groups in Aromatic Systems
AU - Irle, S.
AU - Krygowski, T. M.
AU - Niu, J. E.
AU - Schwarz, W. H.E.
PY - 1995/10/1
Y1 - 1995/10/1
N2 - The nitro and nitroso derivatives of methane, benzene, and Li-phenolate weee theoretically investigated with the help of quantum chemical methods (SCF, MP2). Experimental densities weee examined with the OIAM approach. MP2 geometries weee in excellent agreement with advanced experimental data. Geometries, electron densities, atomic charges, and atomic shapes, bond orders, torsional barriers, and reaction energies were analyzed in order to elucidate the inductive and mesomeric influence of NO in comparison to NO2. These influences behave partly additive with -I(NO) < -I(NO2), partly nonlinear and nonadditive with -M(NO2) < -M(NO). Despite some π-character of the PhNO2 bond, the mesomeric influence of NO2 on a nonsubstituted benzene ring is very small, but becomes enhanced by para-donors or corresponding intermolecular interactions.
AB - The nitro and nitroso derivatives of methane, benzene, and Li-phenolate weee theoretically investigated with the help of quantum chemical methods (SCF, MP2). Experimental densities weee examined with the OIAM approach. MP2 geometries weee in excellent agreement with advanced experimental data. Geometries, electron densities, atomic charges, and atomic shapes, bond orders, torsional barriers, and reaction energies were analyzed in order to elucidate the inductive and mesomeric influence of NO in comparison to NO2. These influences behave partly additive with -I(NO) < -I(NO2), partly nonlinear and nonadditive with -M(NO2) < -M(NO). Despite some π-character of the PhNO2 bond, the mesomeric influence of NO2 on a nonsubstituted benzene ring is very small, but becomes enhanced by para-donors or corresponding intermolecular interactions.
UR - http://www.scopus.com/inward/record.url?scp=0000312287&partnerID=8YFLogxK
U2 - 10.1021/jo00126a025
DO - 10.1021/jo00126a025
M3 - Article
AN - SCOPUS:0000312287
SN - 0022-3263
VL - 60
SP - 6744
EP - 6755
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 21
ER -