Characterization of 2,5-diaryl-1,3,4-oxadiazolines by multinuclear magnetic resonance and density functional theory calculations. Investigation on a case of very remote Hammett correlation.
Two series of 2,5-diaryl-1,3,4-oxadiazolines have been studied by multinuclear magnetic resonance and density functional theory calculations. A full NMR spectroscopic characterization has been performed and excellent remote Hammett correlations (sigma(p) or sigma(p)+) have been found for para substitution in the two aryl rings through at least 11 bonds, notwithstanding the presence in the path of atoms that should act as insulators and a lack of correlation for some of the intermediate atoms. The computational investigation on the electronic delocalization, performed with the ACID (anisotropy of the induced current density) method, reveals indeed that electrons are delocalized in almost the entire molecule despite the presence of the insulators.
Cerioni
Giovanni
G
Dipartimento di Scienze Chimiche, Università di Cagliari, Complesso Universitario, S.S. 554, Bivio per Sestu, I-09042 Monserrato (CA), Italy. cerioni@unica.it
Maccioni
Elias
E
Cardia
Maria Cristina
MC
Vigo
Sara
S
Mocci
Francesca
F
D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D055601:Organic Chemistry Phenomena; D010069:Oxadiazoles / Q000737:chemistry*
D010069:Oxadiazoles; C012466:oxadiazon