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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。
Quantum chemical ab initio calculations were performed on the [Co (triamine) (diamine) Cl] complex [Co (pema) (amp) Cl] 2 + Ten possible geometrical isomers of [(pema) (OH) 2 + (pema = N - (2-pyridylmethyl) ethylenediamine, amp = 2 - (aminomethyl) pyridine) (Four and six areomers) and the calculation of ground state energy. For the [Co (pema) (Cl)] 2 + system, f2 ’; f3; The energy of one isomer is lower than that of other isomers, of which f3 is the lowest. Structurally, they all contain C-H ... π structures. In the synthesis experiment, only the isomer f3 was isolated. For the system Co (pema) (OH) 2 +, the lower ground state energy is still f2 ’; f3; m3; m4, but f3 is the highest one at this time. The four isomers were isolated by the method of equilibrium alkaline hydrolysis. The structural analysis confirmed that they are the four isoforms f2 ’, f3, m3 and m4 with lower energy in the theoretical calculation. This indicates that C-H ... π interaction plays an important role in the formation of the dominant configuration of the system.