Mj. Potrzebowski et al., CORRELATION OF P-31 CHEMICAL-SHIFT PARAMETERS TO MOLECULAR-STRUCTURESOF HEXACOORDINATE ORGANOPHOSPHORUS COMPOUNDS IN THE SOLID-STATE, Perkin transactions. 2, (6), 1995, pp. 1149-1153
P-31 principal elements of chemical shift tensors delta(ii) for a seri
es of hexacoordinate organophosphorus compounds have been obtained fro
m spinning sideband intensities employing the MASNMR program based on
a graphical method of Berger and Herzfeld. It was found that anisotrop
y parameters Delta delta and span Omega reflect the distortion of the
molecular structure from the ideal octahedral geometry. The asymmetry
parameter eta and skew kappa suggest that the phosphorus shielding dep
ends not only on the local bonding, but also on the octahedral structu
re as a whole. Comparison of isotropic chemical shifts in solution and
in solids revealed that in both phases the molecular structures are n
ot changed. Moreover, this work shows that for P-VI moieties with unkn
own X-ray structure, crucial information regarding the geometry can be
obtained from solid-state NMR data and a molecular modelling approach
.