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Titration Calorimetry System for Measurement of Formation Enthalpies of Organometal Complexes

Research Project

Project/Area Number 12554025
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Inorganic chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

ISHIGURO Shin-ichi  Kyushu Univ., Faculty of Science, Professor, 大学院・理学(系)研究科(研究院), 教授 (80111673)

Co-Investigator(Kenkyū-buntansha) UMEBAYASHI Yasuhiro  Kyushu Univ., Faculty of Science, Assistant, 大学院・理学(系)研究科(研究院), 助手 (90311836)
Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥13,200,000 (Direct Cost: ¥13,200,000)
Fiscal Year 2001: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2000: ¥9,400,000 (Direct Cost: ¥9,400,000)
KeywordsTitration Calorimetry / Thermodynamics / Enthalpy of transfer / Silver(I) / PPh_3 complex / Nonaqueous Solvent / 滴定カロリメトリー / 熱測定 / 溶媒和 / パラジウム
Research Abstract

With the aim of calorimetric measurement for the formation of organo-transition metal complexes, we prepared a new vessel for titration calorimetry. The volume of initial test solution is reduced to 4 ml with a new vessel (2 cmφ x 4 cmh). Heat sensor is a couple of thermistors, which can detect temperature changes by 10^<-5> degree. In the present work, we studied complexation of soft-metal soft-ligand Ag^+-EPh_3 (E = P, As, Sb) systems in acetonitrile, which is a stronger π acceptor but weaker σ donor than dimethyl sulfoxide (DMSO). The formation constant of [Ag(EPh_3)]^+ reduced in the order P > As > Sb, and the mono-, bis-, tris- and tetrakis-PPh_3 complexes are formed in AN. The result is compared with that in pyridine (Py), which is a stronger π acceptor and σ donor than DMSO. The soft Ag^+ ion thus shows a specific dπ-π interaction with AN and Py but not with DMSO. The [Ag(PPh_3)_4]^+ is found in AN but not in DMSO and Py. Enthalpies of transfer of individual [Ag(PPh_3)_n]^+ (n = 0-3) species from DMSO to AN show that the value is close to zero for n=0 and become more positive for the complex with increasing n, indicating that the specific dπ-π Ag^+-AN interaction is weakened by bound PPh_3 ligand. Similarly, enthalpies of transfer of individual [Ag(PPh_3)_n]^+ (n = 0-3) species from DMSO to Py show that the value is negative and large for n=0 and become less negative for the complex with increasing n, and the value is slightly negative for [Ag(PPh_3)_3]^+. This indicates that the specific dπ-π Ag^+-Py interaction is almost disappeared by bound PPh_3 ligand. These facts leads to the conclusion that weakened dπ-π interaction and weak σ donating ability of AN is essential for the formation of tetrahedral [Ag(PPh_3)_4]^+ complex.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (25 results)

All Other

All Publications (25 results)

  • [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)

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

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 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 Sci.. 237. 167-173 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 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
      2001 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
      2001 Final Research Report Summary
  • [Publications] M. Komiya: "Ternary Complexation of Manganese(II) and Cadmium(II) with 1,10-Phenanthroline and Halide or Thiocyanate-N Ions in N,N-Dimethylformamide"J. Solution Chem.. 29. 165-182 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Kodama: "A Calorimetric Study of the Acid Dissociation of the Conjugate Acids of Poly(N-vinylimidazole) and Polyallylamine"Colloid & Polymer Science. 278. 1-7 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R. Kanzaki: "Influence of Charge on Adduct Formation of [M(phen)_3]^<z+> (M=Ru^<2+>, Co^<3+>, Si^<4+>) with 1,10-phenanthroline in Aqueous Solution"Chem. Phys. and Phys. Chem.. 2. 3825-3830 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 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
      2001 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
      2001 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 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(欧文)」より
    • Related Report
      2001 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. 5475-5781 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] S. Ishiguro: "Thermodynamics and structural aspects on the solvation steric effect of lanthanide(III) -Dependence on the ionic size"Coord. Chem. Review. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 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
      2001 Final Research Report Summary
  • [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 monics 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
  • [Publications] M.Komiya: "Ternary complexation of manganese (II) and cadmium (II) with 1,10-phenanthroline and halide or thiocyanato ions in N,N-dimethylformamide"J.Solution Chem.. 29/2. 165-182 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Shin: "Formation of Copper (II) Thiocyanato and Cadmium (II) Iodo Complexes in Micelles of Nonionic Surfactants with varying Polyelethyleneoxide"J.Colloid Interface Chem.. 225. 112-118 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Kanzaki: "Influence of Charge on Adduct Formation of [M(phen)_3]^<2+> (M=Ru^<2+>,Co^<3+>,Si^<4+>) with 1,10-phenanthroline in Aqueous Solution"Chem.Phys.and Phys.Chem.. 2. 3825-3830 (2000)

    • Related Report
      2000 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
      2000 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
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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