Ab initio IGLO calculations of 31P NMR shielding tensors of thiophosphoryl compounds. I—dithiadiphosphetanes and dithioxophosphoranes

✍ Scribed by Kerstin Krüger; Gisbert Grossmann; Ulrich Fleischer; Robert Franke; Werner Kutzelnigg

• Publisher: John Wiley and Sons
• Year: 1994
• Tongue: English
• Weight: 775 KB
• Volume: 32
• Category: Article
• ISSN: 0749-1581
• DOI: 10.1002/mrc.1260321006

✦ Synopsis

Abstract

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 RH, 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.