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Optical Resolution and Its Mechanism of Metal Complexes Based on the Chiral Discrimination Between Ions of the Same Sign

Research Project

Project/Area Number 01540513
Research Category

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

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

Principal Investigator

KOINE Norio  Ehime University, Faculty of Engineering, Lecturer, 工学部, 講師 (20036247)

Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1990: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1989: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsChiral Discrimination / Optical Resolution / Induced Circular Dichroism / Pfeiffer Effect / Chromatography / Pfeiffer(ファイファ-)効果 / 誘起円二色性
Research Abstract

Recently, we have first reported the chromatographic complete optical resolution based on the chiral discrimination between ions of the same sign. The purpose of this work is to elucidate the nature of this unexpected phenomenon.
(1) Column chromatographic optical resolution of twenty-six cobalt (III) racemates were carried out using as a chiral eluent an aqueous solution of [Sb_2 (d-tart) _2]^<2->. More than half of the racemates employed were completely resolved. From the comparison of the elution ordersof enantiomers and separation factors obtained for the racemates, we speculated the discrimination mechanism which was induced by the diastereomeric interaction between the chiral solvent sheaths about the selector and racemate.
(2) Pfeiffer effect of [Cr(ox)_3]^<3-> served by [Sb_2(d-tart)_2]^<2-> and its two analogues, [Cr_2(d-tart)(d-tartH)(bpy or phen)_2]^- and the induced CD of the cobalt (III) complexes served by [Sb_2(d-tart)_2]^<2-> were measured. For both chiral discrimination … More phenomena, the observed mean strength is unexpectedly comparable to those obtained for the phenomena between ions of opposite sign. In contrast, the strength are extremely small for the same phenomena served by d-tart^<2-> instead of the three binuclear complexe. These facts is suggestive of a contribution characteristic of the binuclear complexes. Preliminary experiments indicate the formation of liquid-crystalline in a [Cr_2(d-tart)(dtartH)(phen)_2]^- - H_2O system. These facts suggest that a factor of the present discrimination is involved in the solution structure of the binuclear complexes. Under these circumstances, X-ray crystallographic analysis of H[Cr_2(d-tart)(d-tartH)(bpy)_2]・3.5H_2O was performed. It was found that columns are formed in the crystal and the columns are connected by hydrogen bonding with the waters of crystallization. This molecular array suggests the formation of a chiral field in an aqueous solution and is very interesting in connection with the present chiral discrimination mechanism. Less

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Tomoharu Ama: "Metal Complexes of Peptides.IV.Cobalt(III)Complexes with βーAlanylーLーhistidine(Carnosine)Functioning as a Quadridentate Ligand" Bull.Chem.Soc.Jpn.62. 3464-3468 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Charles A.Green: "Syntheses and Characterization of μーCarboxylatoーO,Oーμーhydroxo Chromium(III) Complexes Containing Amino Acids,Acetate and Nicotinate as Bridging Ligands.Crystal Structure of K_2〔Cr(nta)(OH)(acetateーO,O)Cr(nta)〕・4H_2O" Inorg.Chim.Acta. 176. 87-93 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Chromatographic Optical Resolution Based on the Chiral Discrimination between Ions of the Same Sign,Anionic Cobalt(III) Complex Racemates and Anionic Selector〔Sb_2(dーtart)_2〕^<2ー>" Bull.Chem.Soc.Jpn.(Received Dec.10,1990).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Pfiffer Effect and Induced Circular Dichroism Based on the Chiral Discrimination between Anions" Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Crystal Structure of Hydrogen Bis(μーdーtartrato)bis(2,2'ーdipyridyl)dichromate(III)hemiheptahydrate,H〔Cr_2(dーtart)ー(dーtartH)(bpy)_2〕・3.5H_2O" Inorg.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Tomoharu Ama: "Metal Complexes of Peptides. IV. Cobalt (III) Complexes with beta-Alanyl-L-histidine (Carnosine) Functioning as a Quadridentate Ligand" Bull. Chem. Soc. Jpn.62-11. 3464-3468 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Charles A. Green: "Syntheses and Characterization of mu-Carboxylato-O, O-mu-hydroxo Chromium (III) Complexes containing Amino Acids, Acetate and nicotinate as Bridging Ligands. Crystal Structure of K_2[Cr(nta)(OH)(acetate-O, O)Cr(nta)]・4H_2O" Inorg. Chim. Acta. 176-9. 87-93 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Chromatographic Optical Resolution Based on the Chiral Discrimination between Ions of the same sign, Anionic Cobalt (III) Complex Racemates and Anionic Selector [Sb_2(d-tart)_2]^<2->" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Pfeiffer Effect and Induced Circular Dichroism Based on the Chiral Discrimination between Anions" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Norio Koine: "Crystal Structure of Hydrogen Bis(mu-d-tartrato)bis(2, 2'-dipyridel)-dichromate (III) hemiheptahydrate, H[Cr(d-tart)-(d-tartH)(bpy)_2]・3.5H_2O" Inorg. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Charles A.Green: "Syntheses and Characterization of μーCarboxylatoーO,Oーμーhydroxo Chromium(III) Complexes Containing Amino Acids,Acetate and Nicotinate as Bridging Ligands.Crystal Structure of K_2[Cr(nta)(OH)(acetateーO,O)Cr(nta)]・4H_2O" Inorg.Chim.Acta. 176. 87-93 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Norio Koine: "Chromatographic Optical Resolution Based on the Chiral Discrimination between Ions of the Same Sign,Anionic Cobalt(III) Complex Racemates and Anionic Selector [Sb_2(dーtart)_2]^<2->" Bull.Chem.Soc.Jpn.

    • Related Report
      1990 Annual Research Report
  • [Publications] Norio Koine: "Pfeiffer Effect and Induced Circular Dichroism Based on the Chiral Discrimination between Anions" Bull.Chem.Soc.Jpn.

    • Related Report
      1990 Annual Research Report
  • [Publications] Norio Koine: "Crystal Structure of Hydrogen Bis(μーdーtartrato)bis(2,2'ーdipyridyl)dichromate(III) hemiheptahydrate,H[Cr_2(dーtart)ー(dーtartH)(bpy)_2]・3.5H_2O" Inorg.Chem.

    • Related Report
      1990 Annual Research Report
  • [Publications] Tomoharu Ama: "Metal Complexes of Peptides IV.Cobolt(III)Complexes with β-Alanyl-L-histidine(Carnosine)Functioning as a Quadridentate Liqand." Bull.Chem.Soc.Jpn.,. 62. 3464-3468 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Norio Koine: "Chromatographie Optical Resolution of Anionic Cobalt(III)Complexes bared on Chiral Discrimination bitween Ions of The Same Sign." Bull.Chem.Soc.Jpn.,.

    • Related Report
      1989 Annual Research Report
  • [Publications] Norio Koine: "Pfeiffer Effect and Induced Circutan Dichroism bared on Chiral Discrimination between Anions" Chem Lett.,.

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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