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Contributions of Solute-Solvent Interactions to Ion Selectivity of Macrocyclic Ligands

Research Project

Project/Area Number 15550062
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Analytical chemistry
Research InstitutionChiba University

Principal Investigator

KATSUTA Shoichi  Chiba University, Faculty of Science, Associate Professor, 理学部, 助教授 (40277273)

Co-Investigator(Kenkyū-buntansha) TAKEDA Yasuyuki  Chiba University, Faculty of Science, Associate Professor, 理学部, 教授 (30111412)
KUDO Yoshihiro  Chiba University, Faculty of Science, Associate Professor, 理学部, 助教授 (00195463)
Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥3,100,000 (Direct Cost: ¥3,100,000)
KeywordsComplex Stability Constants / Transfer Activity Coefficients / Alkali Metal Ion s / Crown Ethers / Selectivity / Solvent Effects / Solute-Solvent Interactions
Research Abstract

Stability constants of 1:1 complexes of dibenzo-3m-crown-m(m=6,7,8,10) with alkali metal ions (Na^+,K^+,Rb^+,Cs^+) have been determined at 25℃ in water, nitromethane, and a few nonaqueous solvents by capillary electrophoresis or conductometry. The selectivities of these crown ethers in acetonitrile, propylene carbonate, methanol, N,N-dimethylformamide and water often obey cavity-size/ion-size relationship. On the other hand, the stability constants in nitromethane, which has the weakest solvation power for the metal ions, decrease with increasing ionic size (Na^+>K^+>Rb^+>Cs^+), reflecting the gas-phase selectivity governed by the electrostatic interaction between the ether oxygen atoms and the metal ion. It follows from this that the selectivities of these crown ethers in the solvents other than nitromethane are largely due to the solute-solvent interactions. The transfer activity coefficients of the crown ethers and their alkali metal ion complexes from nitromethane to the other polar solvents have been determined to evaluate the solvation of these solutes. It is shown that the crown ethers shields the alkali metal ions effectively from the solvents; the shielding is generally more effective for the larger crown ether. The solvent effects on the selectivities of the crown ethers are attributed to the solvation of the free metal ions.

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (19 results)

All 2005 2004 2003 Other

All Journal Article (18 results) Publications (1 results)

  • [Journal Article] Stability and solvation of alkali metal ion complexes with dibenzo-30-crown-102005

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Inorganica Chimica Acta 358・3

      Pages: 713-719

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Stability and transfer activity coefficients from water to polar nonaqueous solvents of 1,2-bis[2-(2-methoxyethoxy)ethoxy]benzene-and benzo-18-crown-6-cation complxes2005

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Coordination Chemistry 58・4

      Pages: 373-379

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stability and Solvation of 1:1 Complexes of Dibenzo-21-crown-7 with Alkali Metal Ions in Polar Solvents2005

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Journal of Chemical & Engineering Data (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stability and solvation of alkali metal ion complexes with dibenzo-30-crown-102005

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Inorganica Chimica Acta 358(3)

      Pages: 713-719

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stabilities and transfer activity coefficients from water to polar nonaqueous solvents of 1,2-bis[2-(2-methoxyethoxy)ethoxy]benzene-and benzo-18-crown-6-cation complexes2005

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Coordination Chemistry 58(4)

      Pages: 373-379

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stabilities and transfer activity coefficients from water to polar nonaqueous solvents of 1,2-bis[2-(2-methoxyethoxy)ethoxy]benzene- and benzo-18-crown-6-cation complexes2005

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Coordination Chemistry 58・4

      Pages: 373-379

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents2004

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Inorganica Chimica Acta 357・2

      Pages: 541-547

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Study on solute-solvent and solute-solute interactions for the dibenzo-24-crwon-8-alkali metal picrate extraction system2004

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Molecular Liquids 115・2-3

      Pages: 139-147

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Equilibrium studies on aqueous ion-pair formation and m-xylene/water distribution of tetraalkylammonium picrates2004

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Journal of Solution Chemistry 33・5

      Pages: 437-451

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 and dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents2004

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Inorganica Chimica Acta 357(2)

      Pages: 541-547

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Study on solute-solvent and solute-solute interactions for the dibenzo-24-crown-8-alkali metal picrate extraction system2004

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Molecular Liquids 115(2-3)

      Pages: 139-147

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Equilibrium studies on aqueous ion-pair formation and m-xylene/water distribution of tetraalkylammonium picrates2004

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Journal of Solution Chemistry 33(5)

      Pages: 437-451

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stabilities in nitromethane of alkali metal ion complexes with dibenzo-l8-crown-6 and dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents2004

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Inorganica Chimica Acta 357・2

      Pages: 541-547

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Study on solute-solvent and solute-solute interactions for the dibenzo-24-crown-8-alkali metal picrate extraction system2004

    • Author(s)
      Yasuyuki Takeda
    • Journal Title

      Journal of Molecular Liquids 115・2-3

      Pages: 139-147

    • Related Report
      2004 Annual Research Report
  • [Journal Article] (総合論文)クラウンエーテル及びそのアルカリ金属イオン錯体の水一極性非水溶間移行活量係数2003

    • Author(s)
      勝田 正一
    • Journal Title

      分析化学 52・2

      Pages: 89-105

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Transfer activity coefficients of crown ethers and their alkali metal ion complexes between water and polar nonaqueous solvents(Japanese)2003

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Bunseki Kagaku 52(2)

      Pages: 89-105

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stability and solvation of 1:1 complexes of dibenzo-21-crown-7 with alkali metal ions in polar solvents

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Journal of Chemical & Engineering data (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stability and Solvation of 1:1 Complexes of Dibenzo-21-crown-7 with Alkali Metal Ions in Polar Solvents

    • Author(s)
      Shoichi Katsuta
    • Journal Title

      Journal of Chemical & Engineering Data (発表予定)

    • Related Report
      2004 Annual Research Report
  • [Publications] Shoichi Katsuta: "Stabilities in nitromethane of alkali metal ion complexes with dibenzo-18-crown-6 and dibenzo-24-crown-8 and their transfer from nitromethane to other polar solvents"Inorganica Chimica Acta. 357・2. 541-547 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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