Our goal is to develop a theoretical methodology for the analysis of P-31 N
MR spectra in vanadium phosphorus oxide (VPO) systems important in heteroge
neous catalysis. Within the framework of density functional theory, we inve
stigate the shielding of the phosphorus nucleus in a series of related comp
ounds. The importance of the basis set is pointed out by looking at the inf
luence of polarization functions on the chemical shift of phosphorus in H3P
O4. Using the B3LYP functional, very good agreement with the experimental i
sotropic shielding is reached for the binuclear species [(VO2)(2)(HPO4)(2,2
'-bipy)(2)] constructed from two edge-sharing dioxovanadium(V) octahedra. A
s a prime motivation, a parent vanadium(V) model of pyrophosphate catalyst
is finally studied to compare P-31 numerical calculations with experiment.
Satisfactory shielding constants are obtained, making phosphorus a probe to
investigate the transition metal environment.