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Chiral Discrimination of Metal Complexes by Their Solubility Phase Diagrams

Research Project

Project/Area Number 60430013
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionOsaka University

Principal Investigator

KOMORITA Takashi (1987-1988)  Assistant professor Department of Chemistry, Faculty of Science, Osaka University, 理学部, 講師 (90028209)

新村 陽一 (1985-1986)  阪大, 理学部, 教授 (60028074)

Co-Investigator(Kenkyū-buntansha) FUYUHIRO Akira  Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (90156951)
YAMANARI Kazuaki  Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (40116124)
MATSUOKA Nobuko  Research Assistant Department of Chemistry, Faculty of Science, Osaka University, 理学部, 助手 (30028203)
小森田 喬志  大阪大学, 理学部, 講師 (90028209)
Project Period (FY) 1985 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥19,000,000 (Direct Cost: ¥19,000,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1986: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1985: ¥15,000,000 (Direct Cost: ¥15,000,000)
KeywordsMetal complex / Solubility phase diagram / Chiral discrimination / Spontaneous resolution / Diastereomer / Optical resolution / Heteropoly acid / シクロデキストリン
Research Abstract

The binary and ternary solubility phase diagrams for the following systems were determined; [Co(leu)(NH_3)_4]Br_2, [CoCO_3(en)_2]Br, (NH_4)_6[Co_2Mo_<10>O_<38>H_4].7H_2O,[Co(diNOsar)]X_3, [Co(Me_2dtc)(en)_2]X_2, and [Co(ox)(en)_2](meso-tart)_<1/2>. Spontaneous resolution was found for [CoCO_3(en)_2]Br and for (NH_4)_6[Co_2Mo_<10>O_<38>H_4 ・7H_2O. The former complex crystallizes sa both a racemic compound (below 15 ゜C) and conglomerate (above 15 ゜C). The latter one is the first heteropoly acid forming a conglomerate. In the ternary phase diagrams of Co(leu)(NH_3)_4 Br_2, the only one isotherm was found and the composition of the solid phase changed according to the solution composition. This means the existence of solid solution, which was supported by the smae IR spectra and X-ray powder patterns of [Co(L-leu)(NH_3)_4]Br_2 and [Co(DL-leu)(NH_3)_4]Br_2. This is very important to clarify the nature of chiral discrimination. Some metal complexes were kinetically resolved by drystallization in the presence of chiral additives. This resolution mechanism is best explained in terms of streoselective adsorption of the chiral additives at the crystal surfaces of one enantiomer with the same absolute configuration as that of the chiral additives. The chromatographic column prepared from SP-Sephadex C-25 resins and -and -( -cyclodextrinato)bis(ethylenediamine)cobalt(III)(1+) chloride could be successfully applied to the optical resolution of anionic complexes containing amino acids.

Report

(5 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • 1986 Annual Research Report
  • 1985 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] Kazuaki,Yamanari: Inorg.Chem.24. 4600-4605 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Nobuko,Matsuoka: Bull.Chem.Soc.Jpn.59. 2151-2155 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoichi,Shimura: Bull.Chem.Soc.Jpn.59. 2913-2914 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoichi,Shimura: Bull.Chem.Soc.Jpn.61. 693-698 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Masakazu,Kita: Bull.Chem.Soc.Jpn.62. 23-32 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Kazuaki,Yamanari: Inorg.Chem.28. 248-252 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Kazuaki,Yamanari: J.Chem.Soc.,Chem.Commun.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Takashi,Komorita: Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Kazuaki,Yamanari: "Kinetic Optical Resolution of Metal Complexes through a Stereoselective Adsorption and Inhibition Mechanism Caused by Chiral Additives" Inorg. Chem.24. 4600-4605 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Nobuko,Matsuoka: "Magnetic Circular Dichroism Spectra of Cobalt(III) Complexes in the Second d-d Absorption Band Region" Bull. Chem. Soc. Jpn.59. 2151-2155 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoichi,Shimura: "Tris(tellurato)cobaltate(III) and Tris(ethylenediamine)tris-(tellurato)tetracobaltate(III) Complexes" Bull. Chem. Soc. Jpn.59. 2913-2914 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] (the late) Yoichi,Shimura: "A Quantitative Scale of the Spectrochemical Series for the Mixed Ligand Complexes of d Metals" Bull. Chem. Soc. Jpn.61. 693-698 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Masakazu,Kita: "The Synthesis and Oxidation of Mixed Cobalt(III) Complexes with Dimethyldithiocarbamato and Diamine Ligands, and the Crystal Structure of (+)^CD_-Dimethyldithiocarbamatobis(ethylenediamine)-cobalt(III) Bis[ -(R,R)-tartrato]diantimonate(III) Pentahydrate" Bull. Chem. Soc. Jpn.62. 23-32 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Kazuaki,Yamanari: "Coordination of Cyclodextrin: Synthesis and Characterization of Two Diastereomers of ( - and -Cyclodextrinato)bis- (ethylenediamine)cobalt(III)(1+) and Their Related Complexes" Inorg. Chem.28. 248-252 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Kazuaki,Yamanari: "Optical Resolution of Anionic Complexes by a Chromatographic Column Containing ( -Cyclodextrinato)bis(ethylenediamine)- cobalt(III)(1+) Chloride" J. Chem. Soc., Chem. Commun.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Takashi,Komorita: "Electronic Spectra of Square-Planar Bis(biuretato)cobaltate(III)- Type Complexes" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoichi,Shimura: Bull.Chem.Soc.Jpn.61. 693-698 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Masakazu,Kita: Bull.Chem.Soc.Jpn.62. 23-32 (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] Kazuaki,Yamanari: Inong.Chem.28. 248-252 (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] Kazuaki,Yamnari: J.Chem.Soc.,Chim.Commun.

    • Related Report
      1988 Annual Research Report
  • [Publications] Takashi,Komorita: Bull.Chem.Soc.Jpn.

    • Related Report
      1988 Annual Research Report
  • [Publications] M. Kita, K. Yamanari, Y. Shimura: Bull. Chem. Soc. Jpn.

    • Related Report
      1987 Annual Research Report
  • [Publications] T. Komorita, M. B. Fujita, K. Kanamori, S. Hayashi, Y. Shimura: Bull. Chem. Soc. Jpn.

    • Related Report
      1987 Annual Research Report
  • [Publications] Kazuaki Yamanari: Inorg.Chem.24. 4600-4605 (1985)

    • Related Report
      1986 Annual Research Report
  • [Publications] Yoichi Shimura: Bull.Chem.Soc.Jpn.59. 2913-2914 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] Kazuaki Yamanari: Inorg.Chem.

    • Related Report
      1986 Annual Research Report
  • [Publications] Akira Fuyuhiro: Bull.Chem.Soc.Jpn.

    • Related Report
      1986 Annual Research Report
  • [Publications] Inorganic Chemistry. 24-26. (1985)

    • Related Report
      1985 Annual Research Report

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

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