Abstract
To understand the substitution effects of 2-acylpyridine on the reaction equilibrium, the coordination interaction between a series of 2-acylpyridine derivatives and peroxovanadium(V) complex [OV(O2)2(D2O)]−/[OV(O2)2(HOD)]− in solution was explored by the combined use of multinuclear (1H, 13C, and 51V) magnetic resonance, COSY, together with HSQC in 0.15 M NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 2-acylpyridine derivative ligands is 2-acetylpyridine (1) > 2-propionylpyridine (2) > 2-butyrylpyridine (4) > 2-isobutyrylpyridine (3). The competitive coordination results in the formation of a series of new seven-coordinate peroxovanadium species [OV(O2)2L]− (L = 1, 2, 3, and 4). The results of density functional calculations indicated that the solvation effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 2-acylpyridine derivative.
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