title: Study of stereospecificity of 1H, 13C, 15N and 77Se shielding constants in the configurational isomers of the selenophene-2-carbaldehyde azine by NMR spectroscopy and MP2-GIAO calculations.
abstract: In the (1)H and (13)C NMR spectra of selenophene-2-carbaldehyde azine, the (1)H-5, (13)C-3 and (13)C-5 signals of the selenophene ring are shifted to higher frequencies, whereas those of the (1)H-1, (13)C-1, (13)C-2 and (13)C-4 are shifted to lower frequencies on going from the EE to ZZ isomer or from the E moiety to the Z moiety of EZ isomer. The (15)N chemical shift is significantly larger in the EE isomer relative to the ZZ isomer and in the E moiety relative to the Z moiety of EZ isomer. A very pronounced difference (60-65 mg/g) between the (77)Se resonance positions is revealed in the studied azine isomers, the (77)Se peak being shifted to higher frequencies in the ZZ isomer and in the Z moiety of EZ isomer. The trends in the changes of the measured chemical shifts are reasonably reproduced by the GIAO calculations at the MP2 level of the (1)H, (13)C, (15)N and (77)Se shielding constants in the energy-favorable conformation with the syn orientation of both selenophene rings relative to the C = N groups. The NBO analysis suggests that such an arrangement of the selenophene rings may take place because of a higher energy of some intramolecular interactions.
authors: Institute of Chemistry, Siberian Branch of the Russian Academy of Science, Favorski St 1, 664033 Irkutsk, Russia.
authors: Andrei V
authors: AV
authors: Afonin
authors: Dmitry V
authors: DV
authors: Pavlov
authors: Alexander I
authors: AI
authors: Albanov
authors: Ekaterina P
authors: EP
authors: Levanova
authors: Galina G
authors: GG
authors: Levkovskaya
mesh_terms: D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D016566:Organoselenium Compounds / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D012643:Selenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D007554:Isotopes; D016566:Organoselenium Compounds; D011522:Protons; C570010:selenophene-2-carbaldehyde azine; D012643:Selenium