物理化学学报 >> 2009, Vol. 25 >> Issue (09): 1779-1784.doi: 10.3866/PKU.WHXB20090834

研究论文 上一篇    下一篇

双过氧钒配合物与N-乙基咪唑相互作用的NMR研究

于贤勇, 彭洪亮, 黄昊文, 汪朝旭, 郑柏树, 李筱芳, 易平贵, 陈忠   

  1. 湖南科技大学化学化工学院, 理论化学与分子模拟省部共建教育部重点实验室, 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|厦门大学物理系, 固体表面物理化学国家重点实验室, 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:2009-02-10 修回日期:2009-04-27 发布日期:2009-09-03
  • 通讯作者: 易平贵 E-mail:yipinggui@sohu.com

NMR Studies on Interactions between Diperoxovanadate and 1-Ethyl-1H-Imidazole

YU Xian-Yong, PENG Hong-Liang, HUANG Hao-Wen, WANG Zhao-Xu, ZHENG Bai-Shu, LI Xiao-Fang, YI Ping-Gui, CHEN Zhong   

  1. Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education and Hunan Province, 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 of Physical Chemistry of Solid Surface, Fujian Key Laboratory of Plasma and Magnetic Resonance, Department of Physics, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2009-02-10 Revised:2009-04-27 Published:2009-09-03
  • Contact: YI Ping-Gui E-mail:yipinggui@sohu.com

摘要:

为探讨过氧钒配合物中有机配体对反应平衡的影响, 在模拟生理条件下(0.15 mol·L-1 NaCl 溶液), 应用多核(1H、13C 和51V)多维(COSY 和HSQC)核磁共振(NMR)以及变温技术等谱学方法研究双过氧钒配合物[OV(O2)2L]-(L=D2O 或HOD, 与之配位的过氧钒物种简写为bpV)和[OV(O2)2LL']n-{n=1-2, LL'=3-羟基-皮考啉酸根(3-OH-pic), 2-(2'-吡啶)-咪唑(py-im), 1,10-邻菲啰啉(phen), 与它们配位的含钒物种分别简写为bpV(3-OH-pic)、bpV(py-im)和bpV(phen)}与N-乙基咪唑(N-Et-im)的相互作用. 实验结果表明, N-Et-im 与4种双过氧钒配合物反应性从强到弱的顺序为bpV>bpV(3-OH-pic)>bpV(py-im)>bpV(phen). 研究表明, 金属中心上配体的配位能力、空间位阻和分子量等因素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6配位过氧物种[OV(O2)2(N-Et-im)]-的生成.利用上述谱学方法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: 核磁共振, 双过氧钒配合物, N-乙基咪唑, 相互作用

Abstract:

To understand the effects of organic ligands on the reaction equilibrium, interactions between a series of diperoxovanadate complexes [OV(O2)2L]- (L=D2O or HOD, the corresponding peroxovanadate species (bpV)) and [OV(O2)2LL']n-{n=1-2; LL'=3-hydroxyl-picolinate (3-OH-pic), 2-(2'-pyridine)-imidazole (py-im), 1,10-phenanthroline (phen), the corresponding peroxovanadate species bpV(3-OH-pic), bpV(py-im), and bpV(phen)}and 1-ethyl-1H-imidazole (N-Et-im) in solution were explored using multinuclear (1H, 13C, and 51V) magnetic resonance, COSY (correlated spectroscopy), HSQC (heteronuclear single quantum coherence) and variable temperature nuclear magnetic responance (NMR) using 0.15 mol·L-1 NaCl ionic medium to mimic physiological conditions. Experimental results indicated that the reactivity of these four complexes with 1-ethyl-1H-imidazole decreased as follows: bpV>bpV(3-OH-pic)>bpV(py-im)>bpV(phen). The coordinating ability, the steric effect, and the molecular weight of these organic ligands affected the reaction equilibrium. A new six-coordinated peroxovanadate species [OV(O2)2(N-Et-im)]- was formed because of competitive coordination.

Key words: NMR, Diperoxovanadate, 1-Ethyl-1H-imidazole, Interactions

MSC2000: 

  • O641