Hydrolysis of New Transplatin Analogue Containing One Aliphatic and One Planar Heterocyclic Amine Ligand： A Density Functional Theory Study
Hydrolysis of New Transplatin Analogue Containing One Aliphatic and One Planar Heterocyclic Amine Ligand： A Density Functional Theory Study作者机构：Department of Chemistry Jinan University Guangzhou 510532 China
出 版 物：《Chinese Journal of Chemical Physics》 (化学物理学报（英文）)
年 卷 期：2008年第21卷第4期
页 面：346-352页
核心收录：
学科分类：0832[工学-食品科学与工程（可授工学、农学学位）] 08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 083203[工学-农产品加工及贮藏工程]
主 题：Trans platinum anticancer drug Density functional theory Hydrolysis Aliphatic amine ligand Heterocyclic amine ligand
摘 要：Herein we give a theoretical study of the hydrolysis processes of a novel anticancer drug trans-[PtCl2（3-pico）（ipa）] （3-pico=3-methylpyridine, ipa=isopropylamine）. Two different models, model 1 relative to isolated reactant/product （R/P, wherein R=platinum complex＋H2O, P=platinum complex＋Cl^-） and model 2 relative to reactant complex/product complex （RC/PC, wherein RC=（platinum complex）（H2O）, PC=（platinum complex）（CI^-） are employed and the geometric structures are optimized at the B3LYP level of DFT method. It is found that the processes of the reactions follow the established theory for ligand substitution in square planar complexes; the geometries of the transition states （TS） agree with the previous related work and all of the reactions are endothermic. The effects originating from the inclusion of the attacking water/released chloride into the second coordination shell of platinum in RC/PC play an important role in the thermodynamic and kinetic profiles of the reactions, that is, the barrier heights of the reactions of model 2 are increased by -26.3 and -23.8 kJ/mol for step1 and step2 respectively, and the endothermicity is considerably decreased by -420.5 and -771.2 kJ/mol compared to model 1 in the gas phase. The consideration of the bulk solvation effects increase the barrier heights for both steps of model 1 by -27.6 and -6.7 kJ/mol respectively, whereas it reduces the barrier heights by -7.9 and -29.3 kJ/mol for model 2. The reaction energies are all decreased, especially for model i, indicating more stable complexes solvated in the bulk aqueous solution than in the gas phase. Additionally, to get an accurate energy picture of the title complex, the relative free energies derived from the DFT-SCRF （density functional theory self-consistent field） calculations are compared with the relative total energies. The results are that activation energies rise for the first hydrolysis and fall for the second hydrolysis for all the systems, and for all the systems,
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