铝-草酸和铝-麦芽酚手性配合物特性的密度泛函理论研究  

Studies on the properties of aluminium-oxalate and aluminium-maltolate chiral complexes by density functional theory

作　　者：刘丽 张婧[1] 董绍楠 章福平[1] 毕树平[1] LIU Li;ZHANG Jing;DONG Shaonan;ZHANG Fuping;BI Shuping(School of Chemistry and Chemical Engineering,Nanjing University,Nanjing,210023,China)

机构地区：[1]南京大学化学化工学院,南京210023

出　　处：《环境化学》2018年第9期1928-1939,共12页Environmental Chemistry

基　　金：国家自然科学基金(21177054)资助~~

摘　　要：手性物质广泛存在于环境和生物体中,探讨环境体系中手性金属-有机配合物特性具有重要科学意义.本文采用密度泛函理论(DFT)结合团簇模型(CM)的量子化学计算方法,在B3LYP/6-311+G(d,p)基组水平下,以铝-草酸和铝-麦芽酚为典型实例,研究手性"铝-有机配合物"的动静态性质,系统地开展了以下工作:(1)优化得到了1对铝-草酸和3对铝-麦芽酚手性配合物,并通过静态结构参数、能量参数和谱学性质分析了手性配合物之间的差异;(2)模拟了手性配合物可能存在的10条水交换反应路径,对比了手性配合物水交换反应速率常数;(3)通过Berny方法得到了铝-草酸手性配合物异构体构型转化的动态反应路径,并计算了对映体构型转化的活化能.结果表明,手性对映体具有基本相同的静态结构和能量特征,但偶极矩存在明显差异;溶剂效应对手性对映体静态结构特征、偶极矩和动态水交换反应速率均有影响;手性对映体之间可发生构型相互转化从而改变对映体所占比例.Chiral substances widely exist in the environment and organisms. It is of great scientific significance to investigate the characteristics of chiral metal-organic complexes in environment. In this work,density functional theory（ DFT） calculations combined with cluster model（ CM） were performed at B3 LYP/6-311＋G（ d,p） level to investigate the chiral＂aluminium-organic complexes＂.Using both aluminium-oxalate and aluminium-maltolate complexes as examples,systematic studies on the static and dynamic properties of chiral＂aluminium-organic complexes＂were conducted. Static configurations for one pair of aluminium-oxalate and three pairs of aluminium-maltolate chiral complexes were optimized to obtain their static structure parameters and energetic parameters,as well as spectroscopic properties. Ten possible water-exchange reaction pathways were obtained and the water-exchange rate constants are predicted. Chirality inversion pathway for aluminium-oxalate was simulated using Berny algorithm,and the activation barrier was obtained. The results show that the static structure parameters and energetic parameters of the enantiomers are basically same,but there are obvious differences in the dipole moment. The static structure parameters,dipole momentand the water-exchange rate constants are affected by the solvent effect. The inversion of enantiomers will happen in the environment,leading to the change in the proportion of chiral enantiomers.

关 键 词：手性“铝-有机配合物” 水交换反应 构型转化 密度泛函理论 

分 类 号：O641.4[理学—物理化学]