中文摘要：

为了探讨有机配体上取代基团对反应平衡的影响，在模拟生理条件T（0．15mol／LNaCI溶液），应用多核（^1H，^13C和^51V）多维（COSY和DOSY）NMR以及变温技术等谱学方法研究双过氧钒配合物[OV（O2）2（D2O）]^-/[OV（O2）2（HOD）]^-与N-取代皮考啉酰胺的相互作用．它们反应性从强到弱的顺序为：N-甲基-皮考啉酰胺≈N-（2-羟乙基）-皮考啉酰胺〉N-乙基-皮考啉酰胺〉N-丙基-皮考啉酰胺，这说明了皮考啉酰胺N上取代基的电子效应影响反应．竞争配位导致一系列新的7配位的过氧钒物种生成，而利用上述谱学方法则有助于揭示此类相互作用体系的反应过程和配位机制．

英文摘要：

To understand the substituting effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV（O2）2（D20）]^-/[OV（O2）2（HOD）]^- and a series of N-substituted picolinamide ligands in solution were explored using multinuclear （^1H, ^13C, and ^51V） magnetic resonance, COSY, 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 picolinamide-like ligands with [OV（O2）2（D20）]^-/ [OV（O2）2（HOD）]^- is as follows： N-methylpicolinamide ~ N-（2-hydroxyethyl）picolinamide 〉 N-ethylpicolinamide 〉N-propylpicolinamide. The substituting group influences the reactivity by an electron effect. Competitive coordination interactions result in a series of new seven-coordinated peroxovanadate species [OV（O2）2L]^- （L=N-substituted picolinamide）.