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为探讨取代基团和杂环类型对反应平衡的影响,在模拟生理条件下(0.15 mol/LNaCl溶液),应用多核(1H、13C和51V)NMR技术研究双过氧钒配合物NH4[OV(O)2(2picolinamide)].H2O(简写为bpV(picamd),其中picamd为皮考林酰胺)与唑系配体的相互作用,研究表明bpV(picamd)与有机配体有较强的的反应性,其从强到弱的顺序为:咪唑>2-甲基咪唑>吡唑≈3-甲基吡唑,这说明咪唑类配体的配位能力强于吡唑类,咪唑环上2位取代基影响反应,而吡唑环上3位取代基团不影响反应;竞争配位导致一系列新的6配位过氧钒物种[OV(O)22L]-(L=唑系配体)生成.
In order to investigate the effect of substituent groups and heterocycle types on the reaction equilibrium, multi-nuclear (1H, 13C and 51V) NMR techniques were used to study the effects of diperoxo vanadium complex NH4 [OV (0.15 mol / L NaCl) solution under simulated physiological conditions (Picamd), picamd is picolin amide) and azole ligands, the study shows that bpV (picamd) and organic ligands have a strong reaction The order from strong to weak is: imidazole> 2-methylimidazole> pyrazole ≈3-methylpyrazole, which indicates that the coordination ability of imidazole ligand is stronger than that of pyrazoles, Substituents affect the reaction, while the 3-substituent group on the pyrazole ring does not affect the reaction. Competitive coordination leads to a series of new 6-coordinated vanadyl species [OV (O) 22L] - (L = azole ligand) generate.