论文部分内容阅读
合成了 [Co(bamp)(cmen)Cl]2＋ (bamp=2,6-二甲胺基吡啶； cmen=1,2-二胺基丙烷 )体系的两个经式异构体。利用一维及二维核磁共振 (2D NMR)技术，结合三元胺中吡啶环的磁屏蔽效应，对两个异构体在溶液中的结构进行了解析，对应于 Dowex 50Wx 2柱色层分离的第一色带的阳离子为 m2(cmen的 2位胺基与 Cl处于邻位 );第二色带的阳离子为 m1。由第一色带配合物制备的单晶晶体结构解析也表明其为 m2[ZnCl4]。用量子化学从头计算方法，在赝势基组 RHF/LANL2DZ的水平上研究了该体系两个经式几何异构体的稳定性，结果表明后者较前者稳定，但差别不大，与在合成条件下异构体平衡分布一致。由计算得到的几何优化键参数与晶体结构分析结果能较好地吻合。
Two stereochemicals of the [Co (bamp) (cmen) Cl] 2+ (bamp = 2,6-dimethylaminopyridine; cmen = 1,2-diaminopropane) system were synthesized. The structures of the two isomers in solution were analyzed by 1D and 2D NMR techniques in combination with the magnetic shielding effect of the pyridine ring in the triamines, corresponding to a Dowex 50Wx 2 column chromatography Of the first ribbon has a cation of m2 (the 2-position amine of cmen is in the ortho position with Cl); the second ribbon has a cation of m1. Analysis of the single crystal structure from the first ribbon complex also indicated that it was m2 [ZnCl4]. Quantum chemical ab initio method was used to study the stability of two formal geometric isomers at the pseudo-potential group RHF / LANL2DZ. The results show that the latter is stable, but the difference is not significant, Under the conditions of the equilibrium distribution of isomers. The geometric optimization parameters obtained from the calculation are in good agreement with the results of the crystal structure analysis.