Article ID Journal Published Year Pages File Type
1238164 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2008 6 Pages PDF
Abstract

To understand the substituting group effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV(O2)2(D2O)]−/[OV(O2)2(HOD)]− and a series of 4-substituted pyridines in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, DOSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data are given for the first time. The reactivity among the 4-substituted pyridines is pyridine > isonicotinate > N-methyl isonicotinamide > methyl isonicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L]n− (L = 4-substituted pyridines, n = 1 or 2). The results of density functional calculations provide a reasonable explanation on the relative reactivity of the 4-substituted pyridines. Solvation effects play an important role in these reactions.

Related Topics
Physical Sciences and Engineering Chemistry Analytical Chemistry
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