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Structure of solvent clusters and its effect on metal-ion reactivity in non-aqueous solvent mixtures

Research Project

Project/Area Number 13440222
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 分離・精製・検出法
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

ISHIGURO Shinichi  Kyushu Univ. Faculty of Science Professor, 大学院・理学研究院, 教授 (80111673)

Co-Investigator(Kenkyū-buntansha) UMEBAYASHI Yasuhiro  Kyushu Univ. Faculty of Science Ass. Professor, 大学院・理学研究院, 助教授 (90311836)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2002: ¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 2001: ¥10,300,000 (Direct Cost: ¥10,300,000)
KeywordsSolvation steric effect / N,N-dimethylpropionamide / Tetramethylurea / Enthlpy of transfer / Reaction rate / Comformational change / 配位数 / 滴定ラマン分光 / 回転異性体
Research Abstract

Solvation of the metal-ion and its complexation in some nonaqueous solvents and their mixtures have been studied by means of titration spectrophotometry, catorimetry and Roman spectrometry, all these are on-line controlled for the titration procedure and data acquisition. In the present project, we investigated solvation steric effect (SSE) in the initial and transition states of the metal-ion complexation in nonaqueous solvent mixtures. Solvents used are tetramethylurea (TMU), N,N-dimethylformanmide (DMF), N,N-dimethylacetamide (DMA), N,N-dimethylpropionamide (DMPA), etc. TMU and DMPA show a strong SSE, i.e., the solvation number of the metal ion is reduced, while DMF and DMA show a weak SSE, i.e., the solvation number is kept the same as that in water. It is found that DMPA has two conformational isomers. The two isomers coexist in equilibrium, and the equilibrium constant, and the corresponding enthalpy and entropy values were obtained. The conformational equilibrium largely changes when the solvent molecules simultaneously coordinate to the metal ion, which is ascribed to the conformational change arising from the strong solvation steric effect. This leads to a remarkable difference in the complexation behavior of the manganese(II) ion in TMU and DMPA, despite that the metal ion is five-solvated in both the solvents. The solvation energy of an activated species formed at the transition state of metal-ion complexation is also investigated from the view-point of solvation steric effect. The solvation enthalpy difference of an activated species is defined as the enthalpy of transfer of the activated species from solvent A to B, which is evaluated from the enthalpies of activated measured in the solvents and the enthalpy of transfer of reactants at the initial state from solvent A to B. We found that the solvation steric effect operates significantly at the transition state.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report

Research Products

(34 results)

All Other

All Publications

  • [Publications] Y.Umebayashi: "Raman spectroscopic study on the solvation steric effect of the manganese(II) ion in solvent mixtures of N, N-dimethylformamide and 1,1,3,3-tetramethylurea"J.Mol.Liquid. 103-104. 331-337 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Solvation structure of lanthanide(III) ions in solvent mixtures of N, N-dimethyl-formamide and N, N-dimethylacetamide studied by titration Raman spectroscopy"Chem.Phys.and Phys.Chem.. 4. 5599-5605 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Thermodynamics and structural aspects on the solvation steric effect of lanthanide(III)-Dependence on the ionic size-"Coord.Chem.Review. 226. 103-111 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Metal ion complexation in surfactant solutions"Encyclopedia of Surface and Colloid Science. 3. 3302-3313 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Komiya: "Formation thermodynamics of binary and ternary lanthanide(III) complexes with 1,10-phenanthroline and chloride in N, N-dimethylformanilde"J.Solution Chem.. 32(in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Thermodynamics of [Co(NCS)_4]^<2->at poly(ethylene oxide) and octylphenyl moieties in micelles of nonionic surfactants"J. Colloid & Interface Chem. 237. 167-173 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Individual Solvation Numbers of the Nickel(II) Ion in N, N-Dimethylformamide and N, N-Dimethylacetamide by Raman Spectrophotometry"Anal. Sci.. 17. 323-326 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] R.Kanzaki: "Distribution thermodynamics of 1,10-phenanthroline in nonionic surfactant Triton S-10 micelles"Chem.Phys. And Phys.Chem.. 3. 824-828 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Suzuki: "Complex of cobalt (II) bromide with hexamethylphosphoric triamide"Acta Cryst. C57. 721-722 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Individual solvation number of first-row transition metal(II) ions in solvent mixtures of N, N-dimethylformamide and N, N-dimethylacetamide □ Solvation steric effect-"Chem. Phys. And Phys. Chem. 3. 5475-5481 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Komiya: "Unusual interaction of diiodo complex of zinc (II) with 1,10-phenanthroloine in N, N-dimethylformamide"Phys.Chem.Chem.Phys.. 3. 224-229 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Metal ion complexation in surfactant solutions"Encyclopedia of Surface and Colloid Science. (In press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Thermodynamics of [Co(NCS)_4]^<2-> at poly(ethylene oxide) and octylphenyl moieties in micelles of nonionic surfactants"J. Colloid & Interface Chem.. 237. 167-173 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Individual Solvation Numbers of the Nickel(II) Ion in N,N-Dimethylformamide and N,N-Dimethylacetamide Mixture Determined by Raman Spectrophotometry"Anal. Sci.. 17. 323-326 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] R. Kanazaki: "Distribution thermodynamics of 1,10-phenanthroline in nonionic surfactant Triton X-100 micelles"Chem. Phys. and Phys. Chem.. 3. 824-828 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Suzuki: "Complex of cabalt(II) bromide with hexamethylphosporic triamide"Acta Cryst. C57. 721-722 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Komiya: "Unusual interaction of diiodo complex of zinc(II) with 1,10-phenanthroline in N,N-dimethylformamide"Phys. Chem. Chem. Phys.. 3. 224-229 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Individual solvation number of first-row transition metal(II) ions in solvent mixtures of N,N-dimethylformamide and N,N-dimethylacetamide -Solvation steric efifect-"Chem. Phys. and Phys. Chem.. 3. 5475-5481 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Metal ion complexation in surfactant solutions"Encyclopedia of Surface and Colloid Science. 3302-3313 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Thermodynamics and structural aspects on the solvation steric effect of lanthanide(III)-Dependence on the ionic size-"Coord. Chem. Review. 226. 103-111 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Solvation structure of Ianthanide(III) ions in solvent mixtures of N,N-dimethylformamide and N,N-dimethylacetamide studied by titration Raman spectroscopy"Phys. Chem. Chem. Phys.. 4. 5599-5605 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Raman spectroscopic study on the solvation steric effect of the manganese(II) ion in solvent mixtures of N,N-dimethylformamide and 1,1,3,3-tetramethylurea"J. Mol. Liquid. 103-104. 331-337 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Umebayashi: "Metal ion complexation in surfactant solutions"Encyclopedia of Surface and Colloid Science. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Komiya: "Formation thermodynamics of binary and ternary lanthanide(III) complexes with 1,10-phenanthroline and chloride in N,N-dimethylformamide"J. Solution Chem.. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Umebayashi: "Raman spectroscopic study on the solvation steric effect of the manganese(II) ion in solvent mixtures of N,N-dimethylformamide and 1,1,3,3-tetramethylurea"J. Mol. Liquid. 103-104. 331-337 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Umebayashi: "Solvation structure of lanthanide(III) ions in solvent mixtures of N,N-dimethyl-formamide and N,N-dimethylacetamide studied by titration Raman spectroscopy"Chem. Phys. and Phys. Chem.. 4. 5599-5605 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Umebayashi: "Thermodynamics and structural aspects on the solvation steric effect of lanthanide(III)-Dependence on the ionic size-"Coord. Chem. Review. 226. 103-111 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Umebayashi: "Metal ion complexation in surfactant solutions"Encyclopedia of Surface and Colloid Science. 3. 3302-3313 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Komiya: "Formation thermodynamics of binary and ternary lanthanide(III) complexes with 1,10-phenanthroline and chloride in N,N-dimethylformamide"J. Solution Chem.. 32(in press). (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Kanzaki: "Distribution thermodynamics of 1,10-phenanthroline in nonionic surfactant Triton X-100 micelles"Chem. Phys. and Phys. Chem.. 3. 824-828 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Komiya: "Unusual interaction of diiodo complex of zinc(II) with 1,10-phenanthroline in N, N-dimethylformamide"Chem. Phys. and Phys. Chem.. 3. 224-229 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Umebayashi: "Thermodynamics of [Co(NCS)_4]^<2-> at poly(ethylene oxide) and octylphenyl moieties in micelles of nonionic surfactants"J. Colloid & Interface Sci.. 237. 167-173 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Suzuki: "Complex of cobalt(II) bromide with hexamethylphosphoric triamide"Acta Cryst.. C57. 721-722 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Umebayashi: "Individual solvation number of first-row transition metal(II) ions in solvent mixtures of N, N-dimethylformamide and N, N-dimethylacetamide -Solvation steric effect-"Chem. Phys. and Phys. Chem.. 3. 5475-5481 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-03-31   Modified: 2016-04-21  

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