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Structural trends of 29 Si– 1 H spin–spin coupling constants across double bond
Author(s) -
Rusakov Yury Yu.,
Krivdin Leonid B.,
Nosova Valentina M.,
Kisin Alexander V.,
Lakhtin Valentin G.
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.3860
Subject(s) - chemistry , geminal , antibonding molecular orbital , double bond , coupling constant , delocalized electron , vicinal , bond order , natural bond orbital , spin (aerodynamics) , atomic orbital , crystallography , molecular orbital , steric effects , bond length , computational chemistry , density functional theory , stereochemistry , molecule , physics , crystal structure , electron , thermodynamics , organic chemistry , quantum mechanics
The calculations of geminal and vicinal 29 Si– 1 H spin–spin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second‐order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J ‐coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal 29 Si– 1 H spin–spin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding Si–C and C–H orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding Si–Cl orbitals. Copyright © 2012 John Wiley & Sons, Ltd.