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DFT calculations of 31 P spin–spin coupling constants and chemical shift in dioxaphosphorinanes
Author(s) -
Pecul Magdalena,
Urbańczyk Mateusz,
Wodyński Artur,
Jaszuński Michał
Publication year - 2011
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.2761
Subject(s) - chemistry , heteronuclear molecule , coupling constant , diastereomer , density functional theory , spin (aerodynamics) , chemical shift , computational chemistry , atom (system on chip) , bond length , j coupling , coupling (piping) , crystallography , molecular physics , nuclear magnetic resonance spectroscopy , thermodynamics , stereochemistry , quantum mechanics , crystal structure , physics , mechanical engineering , computer science , engineering , embedded system
One‐bond heteronuclear spin‐spin coupling constants 1 J PX (XH, O, S, Se, C and N) between the phosphorus atom and axial and equatorial substituents in dioxaphosphorinanes are computed using density functional theory (DFT). The experimental values of these coupling constants for a variety of substituents can be applied to identify different diastereoisomers. The DFT calculations confirm the systematic trend observed in experiment, and indicate that the computed 1 J PX coupling constants are related to the length of the axial and equatorial bonds. A similar relation between the phosphorus chemical shift and the R (PX) bond length appears to be valid, with the exception of selenium substituents. Copyright © 2011 John Wiley & Sons, Ltd.