Base Hydrolysis of Pentaaminecobalt(III) Complexes: The [CoX(dien) (dapo)]n+ system. Part 1. Syntheses, structures, configuration, and spectroscopy
作者:Peter Comba、Donald A. House、W. Gregory Jackson、Werner Marty、Helen Stoeckli-Evans、Luc Zipper
DOI:10.1002/hlca.19920750416
日期:1992.6.24
analyses ((−)436(CD)-A (X = N3)), ((−)436(CD)-B). (X = N3), (+)436(CD)-B by their chiroptical properties, and by 13C-NMR spectroscopy supported by 1H-NMR, IR, CD, and UV/VIS spectroscopy. (−)436(CD)-mer-exo(H)-[Co(N3)(dien)(dapo)](hydrogen di-O-benzoyl-L-tartrate)2.4 H2O crystallizes in the orthorhombic space group P212121, a = 7.676(1) Å, b = 19.457(1) Å, c = 34.702(2) Å. (−)436(CD)-mer-endo(H)-[Co(N3)(dien)(dapo)]
在化学计算量的N-(2-氨基乙基)乙烷-1,2-二胺(dien)和1,3-二氨基丙烷-2-醇(dapo)的存在下氧化Co III水溶液可产生μ-过氧钴酸(III)二聚体。酸裂解(HCI)产生mer - exo(H)-,mer - endo(H)-,unsym - fac - exo(OH)-和unsym - fac - endo(OH)-[CoCl(dien)(dapo) ] 2+(A–D)(X = Cl),分别为。和unsym - fac- [Co-(dien)(dapo- N,N ',O)] 3+(G)。通过分步结晶为ZnCl和ClO盐并通过离子交换色谱法可实现异构体分离。还合成了相应的溴,叠氮基,亚硝基-O,硝基-N,硫氰酸根,羟基化合物和水基络合物。制备了用于手性化合物的光学拆分的样品,并通过X射线分析((-)436(CD)-A(X = N 3)),((-)436(CD)-B)对络合物进行了结构表征。(X