Abstract
To understand the substituent effects of 3-picoline derivatives on reaction equilibrium, the interactions between a series of 3-picoline-like ligands and [OV(O2)2(D2O)]−/[OV(O2)2(HOD)]− in solution were explored by multinuclear (1H, 13C, and 51V) magnetic resonance, COSY, and HSQC in 0.15 mol L−1 NaCl ionic medium for mimicking physiological conditions. The relative reactivity among the 3-picoline derivatives is 3-methyl pyridine > nicotinate >nicotinamide > ethyl nicotinate. Competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L] n − (L = 3-picoline derivatives, n = 1 or 2). Density functional calculations provide a reasonable explanation on the relative reactivity of the 3-picoline derivatives. Solvation effects play an important role in these reactions.
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