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Stereochemical behavior of 2 J (Se,H) and 3 J (Se,H) spin‐spin coupling constants across sp 3 carbons: a theoretical scrutiny
Author(s) -
Rusakov Yury Yu.,
Krivdin Leonid B.
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.3838
Subject(s) - geminal , chemistry , vicinal , coupling constant , dihedral angle , lone pair , spin (aerodynamics) , stereospecificity , crystallography , natural bond orbital , computational chemistry , stereochemistry , molecule , quantum mechanics , thermodynamics , density functional theory , organic chemistry , hydrogen bond , physics , catalysis
A theoretical study of geminal and vicinal 77 Se‐ 1 H coupling constants in the benchmark dimethyl and diethyl selenides has been performed at the SOPPA level followed by the NJC analysis within the NBO approach to reveal their stereochemical behavior in respect with the three main structural factors, namely, (i) the dihedral angle dependences, (ii) the bond angle dependences and (iii) the lone pair effects. It has been demonstrated that both geminal and vicinal couplings provide a unique stereospecificity in respect with the orientational lone pair effect together with the geometry of a coupling pathway, which is of prime importance for the stereochemical studies of organoselenium compounds. Copyright © 2012 John Wiley & Sons, Ltd.