title: Open-chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se-1H spin-spin coupling constants.
abstract: Stereochemical structure of nine Z-2-(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second-order polarization propagator approach calculations of their (1)H-(1)H, (13)C-(1)H, and (77)Se-(1)H spin-spin coupling constants together with a theoretical conformational analysis performed at the MP2/6-311G** level. All nine compounds were shown to adopt the preferable skewed s-cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C-S and C-Se bonds of the internal ethenyl group are both skewed s-trans. Stereochemical trends of (77)Se-(1)H spin-spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J-coupling analysis within the framework of the natural bond orbital approach.
authors.affiliation: AE Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia.
authors.forename: Yury Yu
authors.initials: YY
authors.lastname: Rusakov
authors.forename: Leonid B
authors.initials: LB
authors.lastname: Krivdin
authors.forename: Maxim V
authors.initials: MV
authors.lastname: Penzik
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Potapov
authors.forename: Svetlana V
authors.initials: SV
authors.lastname: Amosova
mesh_terms: D007554:Isotopes / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011789:Quantum Theory; D012643:Selenium / Q000737:chemistry*; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry*
chemical_list: D007554:Isotopes; D013440:Sulfides; D012643:Selenium