Premium
Open‐chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77 Se– 1 H spin–spin coupling constants
Author(s) -
Rusakov Yury Yu.,
Krivdin Leonid B.,
Penzik Maxim V.,
Potapov Vladimir A.,
Amosova Svetlana V.
Publication year - 2012
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.3858
Subject(s) - chemistry , coupling constant , spin (aerodynamics) , lone pair , crystallography , computational chemistry , stereochemistry , coupling (piping) , molecule , thermodynamics , organic chemistry , quantum mechanics , physics , mechanical engineering , engineering
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. Copyright © 2012 John Wiley & Sons, Ltd.