波谱学杂志 ›› 2009, Vol. 26 ›› Issue (2): 206-215.

• 研究论文 • 上一篇    下一篇

双过氧钒配合物与2-甲基咪唑相互作用的NMR研究

朱雄斌1;于贤勇2;蔡淑惠2; 陈忠2*   

  1. (1.厦门大学 化学化工学院,化学系, 福建省等离子体与磁共振研究重点实验室,福建 厦门 361005;2.厦门大学 物理系,福建省等离子体与磁共振研究重点实验室,福建 厦门 361005)
  • 收稿日期:2008-11-15 修回日期:2008-11-19 出版日期:2009-06-05 发布日期:2009-12-05
  • 通讯作者: 陈忠

Interactions between Diperoxovanadate and 2-Methyl-imidazole Studied by NMR Spectroscopy

ZHU Xiong-bin1; YU Xian-yong2; CAI Shu-hui2;CHEN Zhong2*   

  1. (1.Department of Chemistry, College of Chemistry and Chemical Engineering,
    Fujian Key Laboratory of Plasma and Magnetic Resonance, Xiamen University, Xiamen 361005, China; 2.Department of Physics, Fujian Key Laboratory of Plasma and Magnetic Resonance, Xiamen University, Xiamen 361005, China)
  • Received:2008-11-15 Revised:2008-11-19 Online:2009-06-05 Published:2009-12-05
  • Contact: CHEN Zhong

摘要: 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)2L]n- {n=1~3, L=oxalate (缩写为oxa), picolinate(缩写为pic), bipyridine(缩写为bipy), 和1,10-phenanthroline(缩写为hen),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2-甲基咪唑(缩写为2-Me-Imi)的相互作用,实验结果表明2-Me-Imi与4种双过氧钒配合物的反应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六配位的过氧物种[OV(O2)2(2-Me-Imi)]-的生成.

关键词: 双过氧钒配合物, 核磁共振(NMR), 2-甲基咪唑, 相互作用

Abstract: To understand the effects of organic ligands on reaction equilibrium, the interactions between diperoxovanadate complexes [OV(O2)2LL′]n-(n=1~3; LL′=oxalate, picolinate, 2,2′-bipyridine, and 1,10-phenanthroline) and 2-methyl-imidazole in 0.15 mol/L NaCl ionic medium, which was used to mimick physiological conditions, were explored using multinuclear (1H, 13C, and 51V) NMR spectroscopy and variable temperature experiments. The experimental results indicated the reactivities of the four diperoxovanadate complexes with 2-methyl-imidazole were as follows: bpV(oxalate)>bpV(picolinate)>bpV(2,2′-bipyridine)>bpV(1,10-phenanthroline). Both the coordination capability and the steric effects of the organic ligands affected reaction equilibrium. New sixcoordinated peroxovanadate species [OV(O2)2(2-methyl-imidazole)]- were formed due to competitive coordination.

Key words: NMR, diperoxovanadate, 2-methyl-imidazole, Interactions

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