摘要
本文合成了[Co(tp)_2(R^1R^2NCH_2CH_2NR^3R^4)]X(tp:2-羟基-2,4,6-环庚三烯-1-酮负离子;R^1～R^4:H或CH_3;X:ClO_4^-或Cl^-)系列三元配合物。用阳离子交换法分离了配合物所有可能的非对映异构体对,以质子核磁共振法推定了非对映异构体对的立体构型,测定了配合物的紫外可见吸收光谱,用逆相高效液相色谱法测定了非对映异构体对的平衡生成比。结果表明,二胺类的分光化学序为:en>Me-en>N,N′-Me_2en>N,N-Me_2en>Me_3en>Me_4en。含有不对称配位氮原子的同一配体,因甲基空间取向不同,而有不同的配体场强度,平衡生成比亦不相同。
The ternary complex series of bis(tropolonato)(N-methyl-substituted ethylenediamine) Cobalt(Ⅲ), [Co(tp)_2 (R^1R^2NCH_2CH_2NR^3R^4]^+(tp=univalent anion of tropolone; R^1～R^4=H or CH_3) were prepared. And all the possible racemic pairs of diastereomers were separated by the cation exchange method. The steric structures of the isomers were charaterized by ~1HNMR method. The isomer distribution at equilibrium were determined by the reversed-phase high performance liquid chromatographic method. The UV spectra of the complexes comfirmed that the spectrochemieal series of the diamines decreased in the order of en>Me-en>N,N'-Me_2en>N,N-Me_2en>Me_3en>Me_4en. The same ligand which contains asymmetrical coordinated nitrogen atom have different ligand field strength and the racemic pairs has different equilibrium isomer distribution. It can be explained that the methyl which is attached to the asymmetrical coordinated nitrogen atom has different steric coordination.
关键词
钴络合物
环庚三烯酚酮
乙二胺
Cobalt complex
Tropolone(P)
Ethanediamine (P)
Synthesis
Diastereoisomerism
Configuration
Ultraviolet spectrophotometry
Proton magnetic resonance (PMR) spectrometry
High-speed liquid chromatography
Reversedphase chromatography
