Multinuclear NMR spectroscopic and theoretical study on the interactions between diperoxovanadate complex and picoline-like ligands.
To understand the substituting effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV(O(2))(2)(H(2)O)](-) and a series of picoline-like ligands in solution were explored using 1D multinuclear ((1)H, (13)C, and (51)V) magnetic resonance, 2D diffusion ordered spectroscopy (DOSY), and variable temperature NMR in 0.15 mol/l NaCl ionic medium for mimicking the physiological conditions. The order of reactive capability of the picoline-like ligands with [OV(O(2))(2)(H(2)O)](-) is found to be picolinamide>N-methylpicolinamide>methyl picolinate>ethyl picolinate approximately propyl picoliniate>isopropyl picolinate. The substituting group influences the reactivity by either steric effect or electron-donating effect. Competitive coordination interactions result in a series of new seven-coordinated peroxovanadate species [OV(O(2))(2)L](-) (L=picoline-like ligands). Their coordination ways were confirmed by density functional calculations.
Department of Physics, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, PR China.
Shuhui
S
Cai
Xianyong
X
Yu
Zhong
Z
Chen
D002244:Carbon / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D010545:Peroxides / Q000737:chemistry*; D010847:Picolines / Q000737:chemistry*; D014638:Vanadates / Q000737:chemistry*
D008024:Ligands; D010545:Peroxides; D010847:Picolines; C091767:diperoxovanadate; D014638:Vanadates; D002244:Carbon; D006859:Hydrogen