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Quantitative Description of Reactivity of Metal Complexes and Its Application to Kinetic Analysis

Research Project

Project/Area Number 13640601
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 分離・精製・検出法
Research InstitutionShizuoka University

Principal Investigator

YAMADA Shinkichi  Shizuoka University, Faculty of Engineering, Professor, 工学部, 教授 (60022737)

Co-Investigator(Kenkyū-buntansha) NAKAMURA Motoshi  Shizuoka University, Faculty of Engineering, Professor, 工学部, 教授 (80022242)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2003: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2002: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2001: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywordscomplexation rate / exchange rate of coordinated water / bound-ligand / electron-donor constant / basicity constant / kinetic analysis / ニッケル(II) / ピリジン類
Research Abstract

From the experimental studies to determine the electron-donor constant E(A) of some multidentate ligands A and the consideration on the effect of each donor atom involved in A on E(A), the following results were obtained.
1.Using monodentate pyridines as A, the coruplexation rate of Ni(II)-A 1:1 complexes with 1,10-phenantroline(phen) was studied ; and the rate constant k_<NiA>, given by d[Ni(phen)^<2+>]/dt=k_<Ni>[Ni^<2+>][phen]+ k_<NiA>[NiA][phen], was determined. With k_<NiA> thus obtained, k_<NiA>^<-H2O>(the exchange rate constant of coordinated water molucule at NiA, and E(A) of the pyridines was estimated. From these studies, it was found that the effect of hydrophobic interaction between A and phen should be taken into account for the estimation of E(A) of the pyridines.
2.Using multidentate pyridines as A, E(A) of these pyridines was estimated in the same way as monodentate pyridines. From these studies, it was found that the effective E(A) of the pyridines is given by the summation of E(X) of each donor atom X involved in A corrected for the effect of vicinal functions.
3.Using phthalic acid, anthranilic acid, o-phenylenedliamine, benzoic acid and aniline as A, the effective E(A) of these ligands is estimated. From these studies, it was found that the same discussion as on pyridines was also applicable to these aromatic ligands and with this effective E(A), the basicity constant of A (H(A)), may be estimated from the correlation logK_<NiA>=αE(A)+βH(A) where K_<NiA> refers to the formation constant of NiA, and α and β are constants characteristic of nickel(II). With the same parameers, the reasonableness of the experimental conditions of our kinetic analysis proposed previously were examined.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] S.Aizawa, Y.Ohishi, S.Yamada, M.Nakamura: "Kinetic Effect of Zinc(II) and Cadmium(II) Ions on Configurational Inversion of Δ_<LLL>-fac(S)-Tris(L-cysteinato-N,S)cobalt(III)"Analytical Sciences. 17. 339-343 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Aizawa, T.Iida, Y.Sone, T.Kawamoto, S.Funahashi, S.Yamada, M.Nakamura: "Thiolato-Ligand Substitution Reaction with Halide Ions of Five-Coordinate Trigonal-Bipyramidal Palladium(II) Complexes with Tris(2-(diphenylphosphino)ethyl)phosphine"Bull.Chem.Soc.Jpn. 75. 91-97 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Aizawa, Y.Sone, T.Kawamoto, S.Yamada, M.Nakamura: "Kinetic Studies on Thiorato-Ligand Substitution Reaction with Halide Ions of Square-Planar Palladium(II) Complex with Bis(2-(diphenylphosphino)ethyl)phosphine"Inorg.Chim.Acta. 338. 235-239 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 山田眞吉(分担執筆, 舟橋重信編): "定量分析-基礎と応用-"朝倉書店. 168(81) (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Aizawa, Y.Ohishi, S.Yamada, M.Nakamura: "Kinetic Effect of Zin c(II) and Cadnium(II) Ions on Configurational Inversion ofΔ_<LLL>-fac(S)-Tris(L-cysteinato-N, S)cobalt(III)"Anal.Sci.. 17. 339-343 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Aizawa, T.Iida, Y.Sone, T.Kawamoto, S.Funahashi, S.Yamada, M.Nakamura: "Thiorato-Ligand Substitution Reaction with Halide Ions of Five-Coordinate Trigonal-Bi-pyramidal Palladium(II) Complexes with Tris-(2-(diphenylphosphino) ethyl)phosphine. Electronic and Steric Effects on the Reaction Mechanism"Bull.Chem.Soc.Jpn.. 75. 91-97 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Aizawa, Y.Sone, T.Kawamoto, S.Yamada, S.Nakamura: "Kinetic Studies on Thiolato-Ligand Sub stitution Reaction with Halide Ions of Square-Planar Palladium(II) Complex with Bis (2-(diphenylphosphino)ethyl)phosphine"Inorg.Chim.Acta. 338. 235-239 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamada: "Quantitative Analysis (in Japanese, partly)"Asakura. (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 山田 眞吉(分担執筆): "定量分析-基礎と応用-(舟橋 重信 編)"朝倉書店. 82 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Aizawa(會澤宣一): "Kinetic Studies on Thiolato-Ligand Substitution Reactions with Haride Ions of Squar Planar Palladium(II) Complexes with pp"Inorg. Chim. Acta. 338C. 235-239 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S. Aizawa(會澤宣一): "Kinetic Effect of Zinc(II) and Cadmium(II) Ions on Configurational Inversion of Δ_<LLL>-fac(S)-Tris(L-cysteinato-N,S)cobalt(III) Complex"Anal. Sci.. 17・2. 339-343 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S. Aizawa(會澤宣一): "Thiolato-Ligand Substitution Reaction with Halide Ions of Five-Coordinate Trigonal-Bipyramidal Pd(II) Complexes with pp_3"Bull. Chem. Soc. Jpn.. 75・1. 91-97 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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