摘要
用量子化学从头计算方法 ,在赝势基组RHF/LANL2DZ的水平上对 [Co(三元胺 ) (二元胺 )Cl]型配合物 - [Co( pema) (amp)Cl]2 +及 [Co( pema) (amp)OH]2 +( pema =N - ( 2 -吡啶基甲基 )乙二胺 ,amp =2 - (氨基甲基 )吡啶 )体系的十个可能的几何异构体 (四个经式异构体和六个面式异构体 )进行了结构优化及基态能量计算 ,对于 [Co( pema) (amp)Cl]2 +体系 ,f2’ ;f3;m3 ;m4四个异构体的基态能量比其他异构体低 ,其中f3为最低。在结构上 ,它们都含有C -H…π结构。而在合成实验中确实仅分离得到异构体f3。对于体系 [Co(pema) (amp)OH]2 +,基态能量较低者仍为f2’ ;f3;m3 ;m4,但此时f3是其中最高者。利用平衡碱水解方法 ,分离提纯得到的四个异构体 ,结构解析证实 ,它们正是理论计算结果中体系能量较低的四个异构体f2’ ,f3,m3和m4。这表明C -H…π相互作用在体系优势构型的形成中起着致关重要的作用。
The computational results for the ten possible geometric isomers (four mer-isomers and six facial-isomers) in the \[Co(ptma)(amp)Cl\] 2+ and \[Co(ptma)(amp)OH\] 2+ systems have been obtained by using an ab initio at RHF/LANL2DZ level (pema = N-(2-pyridylmethyl)ethylenediamine;amp = 2-(Aminomethyl)pyridine) Although the total energies of the isomers f2', f3', m3, m4 are lower than other isomers in these two systems, For the \[Co(ptma)(amp)Cl\] 2+ system, the isomer f3 has the lowest of total energy in the four isomers, however, it is the highest one in the \[Co(ptma)(amp)OH\] 2+ system. Using equilibrate base hydrolysis, three new isomers have been obtained from the isomer f3. It is interpreted as consequences of the C-H...π interaction between the ligands in these isomers.
出处
《贵州大学学报（自然科学版）》
2003年第1期47-51,共5页
Journal of Guizhou University:Natural Sciences
基金
贵州省省长基金资助项目。
