物理化学学报 >> 2007, Vol. 23 >> Issue (11): 1765-1770.doi: 10.3866/PKU.WHXB20071121

研究论文 上一篇    下一篇

咪唑类配体与双过氧钒配合物相互作用的NMR研究

于贤勇; 李国斌; 郑柏树; 黄昊文; 易平贵; 曾云龙; 陈忠   

  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, 湖南 湘潭 411201; 厦门大学固体表面物理化学国家重点实验室, 福建 厦门 361005
  • 收稿日期:2007-05-08 修回日期:2007-07-24 发布日期:2007-11-01
  • 通讯作者: 易平贵; 陈忠 E-mail:yipinggui@sohu.com; chenz@jingxian.xmu.edu.cn

NMR Studies on Interactions between Diperoxovanadate and Imidazole-like Ligands

YU Xian-Yong; LI Guo-Bin; ZHENG Bai-Shu; HUANG Hao-Wen; YI Ping-Gui; ZENG Yun-Long; CHEN Zhong   

  1. Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan Province, P. R. China; State Key Laboratory for Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2007-05-08 Revised:2007-07-24 Published:2007-11-01
  • Contact: YI Ping-Gui; CHEN Zhong E-mail:yipinggui@sohu.com; chenz@jingxian.xmu.edu.cn

摘要: 为探讨咪唑环上取代基团对反应平衡的影响, 在模拟生理条件(0.15 mol·L-1 NaCl溶液)下, 应用多核(1H、13C和51V)、扩散排序谱(DOSY)以及变温NMR等谱学技术研究双过氧钒配合物NH4[OV(O2)2{2-(2’-Pyri-dine)-Imidazole}]·4H2O(简写为bpV(Imi-Py))和咪唑类配体(咪唑、2-甲基鄄咪唑、4-甲基-咪唑和组氨酸)的相互作用, 其从强到弱的顺序为咪唑≈4-甲基-咪唑>2-甲基-咪唑>组氨酸. 研究结果表明, 咪唑环上取代基团空间位阻对反应平衡产生较大影响,同时竞争配位的结果导致新的6 配位过氧物种[OV(O2)2L]-(L 为咪唑类配体)的生成, 当配体为4-甲基-咪唑和组氨酸时, 生成的则是一对异构体.

关键词: 双过氧钒配合物, 咪唑类配体, 相互作用, 核磁共振

Abstract: To understand the substituting effects of imidazole ring on the reaction equilibrium, the interactions between diperoxovanadate complex NH4[OV(O2)2{2-(2’-Pyridine)-Imidazole}]·4H2O (abbr. bpV(Imi-Py)) and a series of imidazole-like ligands (imidazole, 2-methyl-imidazole, 4-methyl-imidazole, and histidine) in solution were explored usingmultinuclear (1H, 13C, and 51V)magnetic resonance, diffusionordered spectroscopy (DOSY), and variable temperature NMR in 0.15 mol·L -1 NaCl ionic medium for mimicking the physiological conditions. The experimental results indicatedthat the activities of bpV(Imi-Py) and organic ligandswere as follows: imidazole≈4-methyl-imidazole>2-methyl-imidazole>histidine. The steric effect of the organic ligands affects the reaction equilibrium. At the same time, newsix-coordinated peroxovanadate species [OV(O2)2L]- (L= imidazole-like ligands) were formed due to the competitive coordination between 2-(2’-pyridyl)-imidazole and the imidazole-like ligands. When the ligand was 4-methyl-imidazole or histidine, a pair of isomers was formed.

Key words: Diperoxovanadate complex, Imidazole-like ligands, Interactions, NMR

MSC2000: 

  • O641