title: Multinuclear NMR and theoretical investigation on interactions between diperoxovanadate complex and 4-picoline-like ligands.
abstract: 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.
authors.affiliation: Department of Physics, Fujian Key Laboratory of Plasma and Magnetic Resonance, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Zhang
authors.forename: Xianyong
authors.initials: X
authors.lastname: Yu
authors.forename: Pinggui
authors.initials: P
authors.lastname: Yi
authors.forename: Haowen
authors.initials: H
authors.lastname: Huang
authors.forename: Shuhui
authors.initials: S
authors.lastname: Cai
authors.forename: Zhong
authors.initials: Z
authors.lastname: Chen
mesh_terms: 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
chemical_list: D008024:Ligands; D010545:Peroxides; D010847:Picolines; C091767:diperoxovanadate; D014639:Vanadium; D014638:Vanadates