Substituent Effects of -NO and -NO2 Groups in Aromatic Systems

S. Irle, T. M. Krygowski, J. E. Niu, W. H.E. Schwarz

Research output: Contribution to journalArticlepeer-review

55 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)6744-6755
Number of pages12
JournalJournal of Organic Chemistry
Volume60
Issue number21
DOIs
StatePublished - Oct 1 1995
Externally publishedYes

Fingerprint

Dive into the research topics of 'Substituent Effects of -NO and -NO2 Groups in Aromatic Systems'. Together they form a unique fingerprint.

Cite this