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
作者单位
梁曜华 澳门药物及健康应用研究所澳门科技大学澳门
中国中医科学院中药研究所北京 100700 
梁国刚 中国中医科学院中药研究所北京 100700 
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5.00,0.15 mol·L-1 NaCl,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。
关键词: 钌化合物  抗转移  水解动力学  稳定性
基金项目: 
Abstract: trans-[RuCl4(DMSO)(N-EtIm)][(N-EtIm)H](N-EtIm=N-ethylimidazole) (compd. 1) was prepared, its hyd-rolytic 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.
Keywords: ruthenium complexes  anti-metastasis  hydrolytic kinetics  stabilities
 
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梁曜华,梁国刚.配体结构对NAMI-A衍生物水解机理、速度的影响[J].无机化学学报,2008,24(12):1983-1988.
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