Multinuclear NMR and theoretical investigation on interactions between diperoxovanadate complex and 4-picoline-like ligands.
To understand the 4-substituting group effects of organic ligands in pyridine ring on the reaction equilibrium, the interactions between a series of 4-picoline-like ligands and [OV(O(2))(2)(D(2)O)](-)/[OV(O(2))(2)(HOD)](-) in solution were explored by the combined use of multinuclear ((1)H, (13)C, and (51)V) 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-picoline-like ligands is 4-picoline>isonicotinate>isonicotinamide>ethyl isonicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O(2))(2)L](n-) (L=4-picoline-like ligands, n=1 or 2). The results of density functional calculations provide a reasonable explanation on the relative reactivity of the 4-picoline-like ligands. Solvation effects play an important role in these reactions.
Zhang
Jun
J
Department of Physics, Fujian Key Laboratory of Plasma and Magnetic Resonance, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen, China.
Yu
Xianyong
X
Yi
Pinggui
P
Huang
Haowen
H
Cai
Shuhui
S
Chen
Zhong
Z
D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008962:Models, Theoretical; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry*; D010847:Picolines / Q000737:chemistry*; D014638:Vanadates / Q000737:chemistry*; D014639:Vanadium / Q000737:chemistry
D008024:Ligands; D010545:Peroxides; D010847:Picolines; C091767:diperoxovanadate; D014639:Vanadium; D014638:Vanadates