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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (16): 1548-1554. 上一篇    下一篇

研究论文

NMR研究N-甲基咪唑与双过氧钒配合物的相互作用

于贤勇1,2, 李国斌1, 郑柏树1, 黄昊文1, 易平贵*,1,2, 彭洪亮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:2007-03-28 修回日期:2007-05-22 发布日期:2007-08-28
  • 通讯作者: 易平贵

NMR Studies on Interactions between Diperoxovanadate Complexes and 1-Methylimidazole

YU Xian-Yong1,2; LI Guo-Bin1; ZHENG Bai-Shu1; HUANG Hao-Wen1; YI Ping-Gui*,1,2; PENG Hong-Liang1; CHEN Zhong*,2   

  1. (1 Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201)
    (2 State Key Laboratory for Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005)
  • Received:2007-03-28 Revised:2007-05-22 Published:2007-08-28
  • Contact: Ping-gui YI

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为探讨过氧钒配合物上有机配体对反应平衡的影响, 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) NMR以及变温技术等谱学方法研究双过氧钒配合物[OV(O2)2LL']n− [n＝1～3, LL'＝oxalate (缩写为oxa)、picolinate(缩写为pic)、bipyridine(缩写为bipy)和1,10-phenanthroline(缩写为phen), 与它们配位的含钒物种分别缩写为bpV(oxa), bpV(pic), bpV(bipy)和bpV(phen)]与N-甲基咪唑(缩写为N-Me-Im)的相互作用, 实验结果表明N-Me-Im与4种双过氧钒配合物的反应活性从强到弱的顺序为: bpV(oxa)＞bpV(pic)＞bpV(bipy)＞bpV(phen). 研究表明金属中心上配体的配位能力和空间位阻都对反应平衡产生较大的影响, 同时竞争配位的结果导致新的过氧物种[OV(O2)2(N-Me-Im)]−的生成, 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方式.

关键词: 双过氧钒配合物, N-甲基咪唑, 相互作用, 核磁共振

To understand the effects of organic ligands of the diperoxovanadate complexes on the reaction equilibrium, the interactions between a series of diperoxovanadate complexes [OV(O2)2LL']n− [n＝1～3; LL'＝oxalate, abbr. oxa; picolinate, abbr. pic; 2,2'-bipyridine abbr. bipy; and 1,10-phenanthroline, abbr. phen. The corresponding peroxovanadate species abbreviate bpV(oxa), bpV(pic), bpV(bipy), and bpV(phen)] and 1-methylimidazole (abbr. N-Me-Im) in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, COSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological conditions. The experimental results indicated the activity order of these four complexes with 1-methylimidazole as follows: bpV(oxa)＞bpV(pic)＞bpV(bipy)＞bpV(phen). Both the coordinating capability and the steric effect of the organic ligands affect the reaction equilibrium. At the same time, a new six-coordinated peroxovanadate species [OV(O2)2(N-Me-Im)]− is formed due to the competitive coordination.

Key words: diperoxovanadate, 1-methylimidazole, interaction, NMR