Development of Optically Active Macro Molecular Metal Complexes

手性大分子络合物如金属酶等具有多种功能性质的手性大分子络合物的合成工艺在各个领域都是人们非常希望得到的。从这个角度出发，我们首先研究了一系列八面体钴(III)配合物的立体化学调控：[Co(Edda类型配体)(手性二胺)]^+。第二，为了寻找一种新型的分子识别体系，我们研究了含双糖N-糖苷配体的镍(II)配合物。对含N-糖苷配体的镍(II)配合物进行了表征，包括X-射线单晶分析。在晶体堆积中，D-麦芽糖衍生的络合阳离子以分子间氢键支撑的新型二聚体形式存在，这可能为通过分子间氢键识别分子提供了基础信息。EFFE…的研制在我们的项目中，在不改变配位球的情况下，对具有潜在有用性质的金属络合物进行更积极的化学修饰是非常必要的。第三，从这个角度出发，我们开发了一种高效的O-酰化金属络合物的O-酰化反应方法。[Co(Dhpta)]^-(式中dhpta=1，3-二氨基-2-羟基丙烷-N，N，N‘，N’-四乙酸阴离子)的非配位羟基与一系列酸酐(醋酸酐、正戊酸酐、苯甲酸酐、邻苯二甲酸酐、丁二酸酐、辛酸酐和十二酸酐)在乙腈中用密码子222溶解后发生O-酰化反应。在非常温和的条件下，在不改变配位范围的情况下获得了相当高的产率。在钴(III)络合物具有长的酰基-(辛基和十二烷基-)链的情况下，形成胶束溶液。最后，我们观察到K[Co(Dhpta)]的非配位羟基通过与作为聚合单体官能团的甲基丙烯酸和丙烯酸酸酐反应而成功地进行了O-酰化。观察了这些化合物水溶液的凝胶化现象。较少

Development of synthetic procedure for chiral macromolecular complexes which show various functional properties like metallo-enzyme are highly desirable in various fields. From this standpoint, at first, we studied a stereochemical regulation of a series of octahedral cobalt(III) complexes : [Co(edda type ligand)(chiral diamine)]^+. We observed remarkable effect of N-alkyl substitutions in the stereoselective formation of the complexes At second, in order to search a new type molecular recognition system, We investigated nickel(II) complexes containing N-glycoside ligands derived from disaccharides. The nickel(II) complexes containing N-glycoside ligands were characterized including X-ray crystallographic analyses. In the crystal packing, the complex cation derived from D-maltose exists in a novel dimeric form supported by intermolecular hydrogen bondings, which might provide fundamental informations concerning molecular recognition via intermolecular hydrogen bond. Development of effe … More ctive chemical modification procedures for metal complexes having potentially useful properties without altering the coordination sphere is highly desirable in our project. At third, from this standpoint, we developed an efficient procedure for O-acylation of a metal complex having a non-coordinated hydroxyl group for the O-acylated complexes. The non-coordinated hydroxyl group of [Co(dhpta)]^-(where dhpta = 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid anion) was O-acylated by reaction with a series of acid anhydrides (acetic anhydride, n-valeric anhydride, benzoic anhydride, phthalic anhydride, succinic anhydride, octanoic anhydride, and dodecanoic anhydride) after the potassium salt of the complex was dissolved in acetonitrile by using cryptand 222. Fairly high yields under remarkably mild conditions were achieved without altering the coordination sphere. In case of cobalt(III) complexes having long acyl-(octyl-and dodecanoyl-) chain form micellar solutions. Finally, we observed that the non-coordinated hydroxyl group of K[Co(dhpta)] was successfully O-acylated by reaction with methacrylic and acrylic acid anhydrides which act as monomer functional group for polymerization. Gelation of aqueous solution of these compounds were observed. Less