Ronald D. Curtis

Applications of Dipolar NMR Spectroscopy in Characterizing Nitrogen and Phosphorus Shielding Tensors

The application of dipolar NMR techniques to the characterization of nitrogen and phosphorus shielding tensors is discussed. After a brief outline of the theoretical basis of the technique, results from the authors’ laboratory are presented. Nitrogen shielding tensors in several compounds containing two-coordinate nitrogen functional groups are characterized and compared to those calculated for related model compounds using the localized orbital-local origin (LORG) method.

Phosphorus-31 NMR studies of stabilized phosphorus ylids in the solid state

Phosphorus-31 powder NMR spectra and high-resolution MAS spectra have been obtained for a number of stabilized phosphorus ylids under conditions of high-power proton decoupling and cross-polarization. The 31P CP/MAS spectra are compared to those obtained from isotropic solutions. The variation of chemical shift anisotropy and of the principal components of the 31P chemical shift tensor determined from 31P powder NMR line shapes are discussed in terms of the relative importance of accepted valence bond resonance structures. The results indicate that the invariance of the isotropic chemical shift, delta iso, observed in previous 31P NMR investigations of phosphorus ylids in solution is due to fortuitous cancellation of opposing changes in the principal components, delta 11 and delta 33, of the 31P chemical shift tensor. The 31P dipolar NMR powder spectrum of a typical stabilized ylid, (C6H5)3(31)P-13CHC(O)OCH2CH3, is analyzed in order to obtain the orientation of the 31P chemical shift tensor with respect to the 31P-13C alpha dipolar vector.