Development of Optically Active Macro Molecular Metal Complexes

光学活性高分子金属配合物的开发

• 批准号: 03555184
• 负责人: YANO Shigenobu
• 金额: $ 4.48万
• 依托单位: NARA WOMEN'S UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555184/
• 关键词: Chemical Modification; Long alkyl chain; Optically active complex; Crystallography; Molecular Recognition; Monomer complex; 長鎖アルキル化; 光学活性錯体; X線結晶構造解析

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

手性大分子配合物具有金属酶等多种功能性质，其合成方法的研究在各个领域都具有重要意义。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：[Co（edda型配体）（手性二胺）]^+的立体化学调控。其次，为了寻找一种新型的分子识别体系，我们研究了含N-糖苷配体的镍（II）配合物。镍（II）配合物含有N-糖苷配体，其特征在于，包括X-射线晶体学分析。在晶体堆积中，D-麦芽糖衍生的配位阳离子以分子间氢键支撑的二聚体形式存在，这可能为分子间氢键识别提供基础信息。发展效应 ...更多信息 在我们的项目中，高度需要具有潜在有用性质而不改变配位球的金属络合物的活性化学改性方法。第三，从这一观点出发，我们开发了一种有效的方法，用于O-酰化的络合物的具有非配位羟基的金属络合物的O-酰化。[Co（dhpta）]^-的非配位羟基（其中dhpta = 1，3-二氨基-2-羟基丙烷-N，N，N '，N'-四乙酸阴离子）通过与一系列酸酐反应而被O-酰化（乙酸酐，正戊酸酐，苯甲酸酐，邻苯二甲酸酐，琥珀酸酐，辛酸酐，和十二烷酸酐）。在相当温和的条件下实现了相当高的产率，而不改变配位圈。在具有长酰基-（辛基-和十二烷酰基-）链的钴（III）络合物的情况下，形成胶束溶液。最后，我们观察到，非配位的羟基K[Co（dhpta）]成功地O-酰化反应与甲基丙烯酸和丙烯酸酐作为单体功能团的聚合。观察到这些化合物水溶液的凝胶现象。少