Development of Optically Active Macro Molecular Metal Complexes

1992 Fiscal Year Final Research Report Summary

• Project/Area Number: 03555184
• Research Category: Grant-in-Aid for Developmental Scientific Research (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: NARA WOMEN'S UNIVERSITY
• Principal Investigator: YANO Shigenobu Nara Women's Univ., Dept. of Chem., Professor, 理学部, 教授 (60011186)
• Co-Investigator(Kenkyū-buntansha): KOMIYA Katsuo TOSO Co LTD, 科学計測事業部, 課長 ; KATO Masako Nara Women's Univ., Dept. of Chem., Assistant, 理学部, 助手 (80214401) ; TSUKAHARA Keiichi Nara Women's Univ., Dept. of Chem., Assistant Professor, 理学部, 助教授 (70112117) ; SATO Mitsunobu Kougakuin Univ.. Dept. of Chem., Lecturer, 工学部, 講師 (10154105)
• Project Period (FY): 1991 – 1992
• Keywords: Chemical Modification / Long alkyl chain / Optically active complex / Crystallography / Molecular Recognition / Monomer complex

Research Abstract

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 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.