Study of (31)P NMR Chemical Shift Tensors and Their Correlation to Molecular Structure

Article abstract of DOI:10.1021/ja00196a015

The nature of the (31)P anisotropic chemical shift interaction is examined by using magic-angle sample spinning NMR.Linear correlations between the principal values of the (31)P chemical shift tensor, P-O bond lengths, and O-P-O bond angles are established.On the basis of a previously established correlation between P-O bond length and d_p-p_O ?-bond order, values of the (31)P chemical shift tensor elements were determined to be linearly related to d_p-p_O ?-bond order.Furthermore, from correlations between bond lengths and bond angles, it was concluded thatfor the phosphates reported in this study the ?- and ?-bond contributions to the (31)P chemical shift interaction are not independent of each other and, hence, cannot be separated into distinct terms.A review of other phosphoryl derivatives suggests that these observations may be general for other quadruply coordinated phosphorus compounds.