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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (21): 2357-2362.    下一篇

研究论文

双过氧钒配合物与N-取代皮考啉酰胺相互作用的NMR研究

李国斌1，于贤勇1,2，郑柏树1，易平贵*,1,2，唐臻强1，陈忠*,2   

  1. (1湖南科技大学化学化工学院 分子构效关系湖南省普通高等学校重点实验室 湘潭 411201)
    (2厦门大学固体表面物理化学国家重点实验室 厦门 361005)
  • 投稿日期:2007-02-03 修回日期:2007-05-28 发布日期:2007-11-14
  • 通讯作者: 陈忠

NMR Studies on Interactions between Diperoxovanadate and N-Substituted Picolinamide

LI Guo-Bin1; YU Xian-Yong1,2; ZHENG Bai-Shu1; YI Ping-Gui*,1,2; TANG Zhen-Qiang1; CHEN Zhong*,2   

  1. (1 Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical En-gineering, Hunan University of Science and Technology, Xiangtan 411201)
    (2 State Key Laboratory for Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005)
  • Received:2007-02-03 Revised:2007-05-28 Published:2007-11-14
  • Contact: CHEN Zhong

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为了探讨有机配体上取代基团对反应平衡的影响, 在模拟生理条件下(0.15 mol/L NaCl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.

关键词: 双过氧钒配合物, N-取代皮考啉酰胺, 相互作用, 核磁共振

To understand the substituting effects of organic ligands on the reaction equilibrium, the interactions between diperoxovanadate complex [OV(O2)2(D2O)]−/[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(D2O)]−/[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).

Key words: diperoxovanadate, N-substituted picolinamide, interaction, NMR