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作 者:梁曜华[1,2] 毕葳[2] 杨滨[2] 赵良[2] 梁国刚[1,2]
机构地区:[1]澳门科技大学,澳门药物及健康应用研究所,中国澳门 [2]中国中医科学院中药研究所,北京100700
出 处:《高等学校化学学报》2011年第2期210-217,共8页Chemical Journal of Chinese Universities
基 金:澳门科技发展基金(批准号:012/2009/A1);国家科技部国际合作基金(批准号:2005DFA30990);中国中医科学院基本科研业务费自主选题项目(批准号:ZZ2006120,Z02089)资助
摘 要:合成了trans-[RuCl4(DMSO)(4-MeIm)][(4-MeIm)H].HCl(4-MeIm=4-甲基咪唑)(1)和trans-[RuCl4(DMSO)(N-MeIm)][(N-MeIm)H](N-MeIm=N-甲基咪唑)(2).通过紫外-可见光谱、核磁共振谱和循环伏安法研究了配体结构(4-甲基咪唑,N-甲基咪唑)对NAMI-A衍生物的水解机理、水解动力学、电化学性质及溶液稳定性的影响.结果表明,化合物1的Ⅰ氯、Ⅱ氯及DMSO水解反应机理与NAMI-A相似,但其各级水解速率皆比NAMI-A快,即将推电子的甲基引入咪唑环(4位)明显加快了NAMI-A衍生物的Ⅰ氯、Ⅱ氯及DMSO水解反应速率.化合物在酸性溶液中的稳定性高于中性溶液.trans-[RuCl4(DMSO)(4-MeIm)][(4-MeIm)H]·HCl(4-MeIm=4-Methylimidazole,1) and trans-[RuCl4(DMSO)(N-MeIm)][(N-MeIm)H](N-MeIm=N-Methylimidazole,2) were synthesized.The influence of ligand structure(4-MeIm and N-MeIm) on hydrolytic mechanism-kinetics,electrochemical properties and solution stabilities of Ru-NAMI-A derivatives was studied by UV,NMR and cyclic voltammetry.The result shows that the 1st and 2nd chloro-hydrolysis as well as DMSO-hydrolysis mechanisms for two compounds are very similar to that for NAMI-A.However,the hydrolytic rates of compound 1 are obviously faster than that of compound 2,which means that introducing electron donating group(methyl) into imidazole ring(C4) of NAMI-A would accelerate hydrolytic reaction of Ru-NAMI-A derivatives.The stability of the complexes in acetic buffer solution is much more stable than that of in neural solution.
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