Spectroscopic investigation of the interaction between diperoxovanadate complexes and benzimidazole-like ligands

To understand the effects of benzimidazole substitution on reaction equilibrium, the interactions between a series of benzimidazole-like ligands and [OV(O2)2(D2O)]−/[OV(O2)2(HOD)]− in solution were explored by a combination of multinuclear (1H, 13C, and 51V) magnetic resonance and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data are reported for the first time. These results show that the relative reactivity among the organic ligands is 2-methyl-1H-benzo[d]imidazole > (1H-benzo[d]imidazol-2-yl)methanol > 1-(1H-benzo[d]imidazol-2-yl)ethanol > 1H-benzo[d][1,2,3]triazole. Both the steric effect and the electron effect of the 2-position substituted groups in benzimidazole ring affect the reaction equilibrium. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L]− (L = benzimidazole-like ligands). Moreover, the results of density functional calculations provided a reasonable explanation on the relative reactivity of the benzimidazole-like ligands as well as the important role of solvation in these reactions.