配体结构对NAMI-A衍生物水解机理、速度的影响  

Influence of Ligand Structure on the Hydrolytic Mechanism and Rate of NAMI-A Derivatives

作　　者：梁曜华[1,2] 梁国刚[2] 

机构地区：[1]澳门药物及健康应用研究所,澳门科技大学 [2]中国中医科学院中药研究所,北京100700

出　　处：《无机化学学报》2008年第12期1983-1988,共6页Chinese Journal of Inorganic Chemistry

基　　金：澳门科技发展基金(No.027/2005/A);国家科技部国际合作基金(No.2005DFA30990)资助。

摘　　要：制备并用紫外-可见分光光度法研究了trans-[RuCl4(DMSO)(N-EtIm)][(N-EtIm)H](N-EtIm=N-乙基咪唑)(化合物1)在pH=7.40及5.00,0.15mol·L-1NaCl,37℃溶液中的水解机理及动力学。化合物1在pH=7.40的缓冲溶液中发生两步水解脱氯反应(Ⅰ氯水解及Ⅱ氯水解)(分步反应),最终溶液颜色变深形成聚合物。在pH=5.00缓冲溶液中二甲基亚砜(DMSO)水解。其Ⅰ氯、Ⅱ氯水解及DMSO水解反应皆为零级反应。测定了各水解反应表观速率常数Kobs及半衰期t1/2。化合物1的Ⅰ氯及Ⅱ氯水解反应与NAMI-A相似,而且各水解速度也相差不大,即将推电子的乙基引入咪唑环,对NAMI-A的Ⅰ氯、Ⅱ氯及DMSO水解反应速度影响较小。化合物在酸性溶液中的稳定性明显高于中性溶液。trans-[RuCh（DMSO）（N-EtIm）][（N-EtIm）H]（N-EtIm=N-ethylimidazole） （compd. 1） was prepared, its hydrolytic mechanism and kinetics were studied by UV-Vis spectroscopy at pH=7.40/5.00, 0.15 mol·L^-1 NaCl, 37 ℃. Compd. 1 undergoes two well-separated steps of chloride hydrolysis at pH=7.40, while dimethyl sulfoxide （DMSO） hydrolyzed in pH=5.00 buffer solution. All the hydrolysis follows the zero order reaction. The Kobs and t1/2 for each reaction were determined. The hydrolytic rate of compd. 1 including 2 chlorides and DMSO hydrolysis are similar to that of NAMI-A, which demonstrates that the influence of introducing ethyl group into imidazole ring is small on the hydrolysis rate of NAMI-A derivatives. The stability of compd. 1 in acidic solution is much more stable than that of in neutral solution.

关 键 词：钌化合物 抗转移 水解动力学 稳定性 

分 类 号：O614.821[理学—无机化学]