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Conformational analysis and stereochemical dependences of 31 P– 1 H spin–spin coupling constants of bis(2‐phenethyl)vinylphosphine and related phosphine chalcogenides
Author(s) -
Fedorov Sergey V.,
Krivdin Leonid B.,
Rusakov Yury Yu.,
Ushakov Igor A.,
Istomitalia V.,
Belogorlova Natalia A.,
Malysheva Svetlana F.,
Gusarova Nina K.,
Trofimov Boris A.
Publication year - 2009
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.2386
Subject(s) - chemistry , phosphine , conformational isomerism , selenide , coupling constant , spin (aerodynamics) , phosphine oxide , crystallography , computational chemistry , sulfide , coupling (piping) , chalcogen , stereochemistry , molecule , organic chemistry , selenium , thermodynamics , mechanical engineering , physics , particle physics , engineering , catalysis
Theoretical energy‐based conformational analysis of bis(2‐phenethyl)vinylphosphine and related phosphine oxide, sulfide and selenide synthesized from available secondary phosphine chalcogenides and vinyl sulfoxides is performed at the MP2/6‐311G** level to study stereochemical behavior of their 31 P– 1 H spin–spin coupling constants measured experimentally and calculated at different levels of theory. All four title compounds are shown to exist in the equilibrium mixture of two conformers: major planar s‐cis and minor orthogonal ones, while 31 P– 1 H spin–spin coupling constants under study are found to demonstrate marked stereochemical dependences with respect to the geometry of the coupling pathways, and to the internal rotation of the vinyl group around the P(X)‐C bonds (X = LP, O, S and Se), opening a new guide in the conformational studies of unsaturated phosphines and phosphine chalcogenides. Copyright © 2009 John Wiley & Sons, Ltd.