• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Stereoselective Interaction and Chiral Discrimination of Transition Metal Complexes

Research Project

Project/Area Number 60470047
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionHIROSHIMA UNIVERSITY

Principal Investigator

HAYAMI Yoneda  Department of Chemistry, Faculty of Science, Hiroshima University, 理学部, 教授 (00031740)

Co-Investigator(Kenkyū-buntansha) HIROSHI Nakazawa  Department of chemistry, Faculty of Science, Hiroshima University, 理学部, 助手 (00172297)
KATSUHIKO Miyoshi  Department of Chemistry, Faculty of Science, Hiroshima University, 理学部, 助手 (60033924)
YOSHIHIKO Kushi  College of General Education, Osaka University, 教養部, 教授 (40033906)
Project Period (FY) 1985 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥7,500,000 (Direct Cost: ¥7,500,000)
Fiscal Year 1986: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1985: ¥7,000,000 (Direct Cost: ¥7,000,000)
Keywordsd-tartrate / chiral discrimination / optical resolution / diasteremeric salt / spontaneous resolution / chromatographic resolution / tetrahedral organometallic complex
Research Abstract

1. The crystal structure analysis was made for three different diastereomeric salts containing <LAMBDA> - <[Co(en)_3]^(3+)> and d- <tart^(2-)> ions, and a unique face-to-face ion-pair structure was found in common in these crystals. This unique ion-pair structure ( <C_3> association) was assumed to be the origin of chiral discrimination.
2. Concerning the mechanism of chiral discrimination by <[Sb_2(d-tart)_2]^(2-)> , the L-J model proposed previously could explain the efficiency of enantiomer separation for a series of <[Co(N)_6]^(3+)> complexes. A concrete hydrogen-bonding association model was newly developed, which can similarly explain the resolution efficiency and is consistent with the CD-spectral studies.
3. Chiral metal complexes were utilized as a selector in the chromatographic resolution of metal complexes A fairly good resolution was actually attained for some neutral metal complexes and the hydrogen-bonding association could be responsible for the chiral discrimination of metal complexes in solution.
4. X-ray structural analysis made for some diastereomeric salts containing <[Sb_2(d-tart)_2]^(2-)> revealed that <[Sb_2(d-tart)_2]^(2-)> approaches <[Co(en)_3]^(3+)> or <[Co(gly)(en)_2]^(2+)> along the (pseudo) <C_3> axis to form triple hydrogen bonds to the axial NH protons. This result supports the hydrogen-bonding association model assumed in the interpretation of chromatographic resolution of <[Co(N)_6]^(3+)> -type complexes.
5. X-ray analysis was made for M[Co(edta)]・n <H_2O> with M = Li,Na,K,Rb,Cs,Mg,Ca,Sr,and Ba, to check if the crystal is spontaneously resolved or not. The results were discussed in terms of various packing modes
6. Chromatographic resolution was attempted for tetrahedral organometallic complexes with no net charge. Induced CD spectra and TLC were found useful to search for optimum conditions of optical resolution.

Report

(1 results)
  • 1986 Final Research Report Summary
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] Hiroshi Okazaki;Yoshihiko Kushi;Hayami Yoneda: J.Am.Chem.Soc.107. 4183-4189 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Katsuhiko Miyoshi;Yukio Sakamoto;Atsuko Ohguni;Hayami Yoneda: Bull.Chem.Soc.Jpn.58. 2239-2246 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hayami Yoneda;Tomoyo Yukimoto;Yoshihiko Kushi;Hiroshi Nakazawa: J.Lig.Chromatogr.9. 573-590 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Katsuhiko Miyoshi;Sinji Izumoto;Hayami Yoneda: Bull.Chem.Soc.Jpn.59. 3475-3482 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Katsuhiko Miyoshi;Sinji Izumoto;Keiji Nakai;Hayami Yoneda: Inorg.Chem.25. 4654-4657 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiroshi Nakazawa;Hisaka Ohtsuru;Hayami Yoneda: Bull.Chem.Soc.Jpn.60. 525-530 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiroshi Okazaki: "Spontaneous Resolution and Polymorphism of Tris(oxalato)cobaltate( <III> ). X-Ray Crystallographic and Thermal Studies" J. Am. Chem. Soc.107. 4183-4189 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Katsuhiko Miyoshi: "Stereoselecitve Interaction of Chiral Metal Complexes in Solution as Studied by Chromatography. I. Modes of Chiral Discrimination and Optical Resolution of Anion Complexes" Bull. Chem. Soc. Jpn.58. 2239-2246 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hayami Yoneda: "Chromatographic Separation of Isomers of Meridional Tris(aminoacidato)cobalt( <III> ) Homochelates and Their Absolute Configuration" J. Liq. Chromatogr.9. 573-590 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Katsuhiko Miyoshi: "Mechanism of Chiral Recognition of Octahedral Metal Complexes Effected by Bis( <mu> -d-tartrato)diantimonate( <III> ) Anion in Solution. <II> . Cage Complexes of the Type <[Co(N)_6]^(3+)> " Inorg. Chem.25. 4654-4657 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiroshi Nakazawa: "Synthesis, Characterization, and Optical Resolution of Electrically Neutral Octahedral Cobalt( <III> ) Complexes Containing the Tetradentate Ligand" Bull.Chem. Soc. Jpn.60. 525-530 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary

URL: 

Published: 1987-03-31   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi