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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (20): 2203-2208. 上一篇    下一篇

研究论文

双过氧钒配合物与3-取代吡啶相互作用的NMR研究

易平贵*,a,b 于贤勇a,b 张 峻b 郑柏树a
黄昊文a,b 曾云龙a 陈 忠b

  

  1. (a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)
    (b厦门大学物理系 固体表面物理化学国家重点实验室 厦门 361005)

  • 投稿日期:2008-02-25 修回日期:2008-05-26 发布日期:2008-10-28
  • 通讯作者: 易平贵

NMR Studies on Interactions between Diperoxovanadate Complex and 3-Substituted Pyridines

YI, Ping-Gui *,a,b YU, Xian-Yong a,b ZHANG, Jun b ZHENG, Bai-Shu a
HUANG, Hao-Wen a,b ZENG, Yun-Long a CHEN, Zhong b
  

  1. (a Hunan College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of
    Science and Technology, Xiangtan 411201)
    (b State Key Laboratory for Physical Chemistry of Solid Surface, Department of Physics, Xiamen University,
    Xiamen 361005)
  • Received:2008-02-25 Revised:2008-05-26 Published:2008-10-28
  • Contact: YI, Ping-Gui

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被引次数

3

为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(DOSY)以及变温NMR技术研究双过氧钒配合物[OV(O2)2(D2O)]－/[OV(O2)2(HOD)]－(简写为dpV)与3-取代吡啶的相互作用, 并首次报道了一些物种的NMR化学位移. dpV与有机配体的反应性从强到弱的顺序为: 吡啶＞烟酸 根＞烟酸甲酰胺≈烟酸甲酯, 这说明吡啶环上取代基影响反应平衡. 竞争配位导致一系列新的6配位的过氧钒物种生成. 密度泛函计算结果合理地解释了实验结果, 并表明溶剂化效应在反应中起重要作用.

关键词: 双过氧钒配合物, 3-取代吡啶, 相互作用, 核磁共振, 理论计算

To understand the substituting group effects of organic ligands on the reaction equilibrium, the interactions between a diperoxovanadate complex [OV(O2)2(D2O)]－/[OV(O2)2(HOD)]－ (abbr. dpV) and a series of 3-substituted pyridines in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, DOSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological condition. Some direct NMR data were given for the first time. The reactivity among the 3-substituted pyridines towards dpV takes the order of pyridine＞nicotinate＞N-methyl nicotinamide≈ methyl nicotinate. The competitive coordination results in the formation of a series of new six-coordinated peroxovanadate species [OV(O2)2L]n－ (L＝3-substituted pyridines, n＝1 or 2). The results of density functional calculations provided a reasonable explanation of the relative reactivity of the 3-substituted pyridines. Solvation effects play an important role in these reactions.

Key words: diperoxovanadate, 3-substituted pyridine, interaction, NMR, theoretical calculation