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Ab initio IGLO calculations of 31 P NMR shielding tensors of thiophosphoryl compounds. I—dithiadiphosphetanes and dithioxophosphoranes
Author(s) -
Krüger Kerstin,
Grossmann Gisbert,
Fleischer Ulrich,
Franke Robert,
Kutzelnigg Werner
Publication year - 1994
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.1260321006
Subject(s) - chemistry , tensor (intrinsic definition) , electromagnetic shielding , ab initio , computational chemistry , principal axis theorem , atomic orbital , ab initio quantum chemistry methods , nuclear magnetic resonance spectroscopy , shielding effect , crystallography , molecule , stereochemistry , geometry , physics , electron , quantum mechanics , organic chemistry , mathematics , layer (electronics)
By means of the IGLO method the 31 P NMR chemical shift, δ iso , the principal values, σ ii , and the orientation of the principal axes of the shielding tensor were calculated for a number of dithiadiphosphetanes [RP(S)S] 2 and of dithioxophosphoranes RPS 2 with RH, CH 3 or C 6 H 5 . The calculated compare well to the available experimental data from solid‐state NMR and can be taken as predictions where no experimental data are available. The dependence of the principal values σ ii on geometry changes and the substitution was studied. The shielding tensors were calculated as sums of contributions of localized molecular orbitals. These contributions were used to discuss the effects observed. They provide valuable insights into relationships between geometrical structure and the principal values of σ.