Open‐chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se–1H spin–spin coupling constants |
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Authors: | Yury Yu. Rusakov Leonid B. Krivdin Maxim V. Penzik Vladimir A. Potapov Svetlana V. Amosova |
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Affiliation: | A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, , 664033 Irkutsk, Russia |
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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 1H–1H, 13C–1H, and 77Se–1H 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 77Se–1H 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. Copyright © 2012 John Wiley & Sons, Ltd. |
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Keywords: | NMR 77Se– 1H spin– spin coupling constants SOPPA NJC analysis unsaturated selanyl sulfides |
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