V-51 NMR chemical shifts have been computed at the GIAO-B3LYP level for non-oxo vanadium(V) complexes related to oxidized amavadin, [Delta-V-V{(S,S)-hidpa}(2)](-) (H(3)hidpa = 2,2'-hydroxyiminodipropionic acid). According to model calculations, the unusual deshielding of the V-51 resonance is due to a combination of conventional substituent effects (e.g., oxo vs dihydroxo or alkoxy vs carboxylato ligands), rather than to a non-innocent nature of the hidpa ligand. For selected diastereomeric vanadium hidpa complexes, Born-Oppenheimer molecular dynamics simulations have been carried out to rationalize the observed differentiation of V-51 NMR chemical shifts. Strongly deshielded V-51 complexes that contain catecholate ligands do show significant disagreement between density functional theory (DFT)-computed chemical shifts and experiment. The possible cause for this deviation is indicated to result from ligand-to-metal charge transfer which can give rise to some open-shell character and temperature-dependent paramagnetic contributions. Electron-withdrawing groups at the catechol moiety tend to increase the corresponding transition energy, thereby reducing these contributions and limiting the non-innocence to the closed-shell ground-state wavefunction.