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1994 Fiscal Year Final Research Report Summary

Mechanistic Study of Metal Complex Formation and Its Application to Kinetic Analysis

Research Project

Project/Area Number 04403011
Research Category

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

Allocation TypeSingle-year Grants
Research Field 分析・地球化学
Research InstitutionNagoya University

Principal Investigator

FUNAHASHI Shigenobu  Nagoya Univ., Faculty of Science, Professor, 理学部, 教授 (30022700)

Co-Investigator(Kenkyū-buntansha) INADA Yasuhiro  Nagoya Univ., Faculty of Science, Research Associate, 理学部, 助手 (60242814)
AIZAWA Sen-ishi  Nagoya Univ., Faculty of Science, Research Associate, 理学部, 助手 (60231099)
Project Period (FY) 1992 – 1994
KeywordsKinetic analysis / Reaction intermediate / Solvation structure / EXAFS method / Stopped-flow method / Porphyrin / Organotin (IV)
Research Abstract

Our purpose is to develop ゙dynamic analytical chemistry゙especially on the basis of dynamic processes of metal complex formation. We proposed the kinetic analyzes on the basis of clarified mechanisms of complexation reactions in aqueous and non-aqueous solutions.The structural analysis of short-lived reaction intermediates was pursued by newly developed techniques. The following research results were obtained.
(1) Techniques to follow the dynamic processes were newly developed such as rapid-injection and high-pressure stopped-flow NMR methods and time-resolved stopped-flow EXAFS methods.
(2) Solvation structures of metal (II,III) ions in solutions were determined by the EXAFS method and the reactivities of the metal ions were clarified on the basis of the pressure effect in terms of bulkiness and chelate effects of solvent molecules.
(3) Deformation effect of the porphine ring on metalloporphyrin formation rate was demonstrated and the reactivity and selectivity of porphyrins for metal ions in kinetic analysis were clarified.
(4) Ternary metal complexes involving oxoacids were investigated in terms of structural aspects and selectivity for analysis.
(5) Structures and reactivities of unstable and short-lived reaction intermediates were successfully determined such as Hg (II) /Cu (II) heterodinuclear porphyrin intermediate, peroxochromium (VI) intermediate, radical intermediate of ascorbic acid, and 5-coordinate chromium (III) porphyrin intermediate.
In conclusion, we presented the trend of dynamic analyzes.

  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] Y.Shimizu et al.: "Kinetic Studies of the Incorporation of the Zine(II)Ion into Water Soluble N-Phenyl-Substituted Porphyrins.Deformation Effect on the Metallation Rate" Bulletin of the Chemical Society of Japan. 65. 771-776 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Soyama et al.: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Study on Solvent Exchange at the Tris(ethylenediamine)nickel(II)Ion in Ethylenediamine" Inorganic Chemistry. 31. 536-538 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Funahashi et al.: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reactions in Solution" Review of Scientific Instruments. 64. 130-134 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aizawa et al.: "Synthesis,Structural Characterization,and Metalation of N-o-Tolyl-5,10,15,20-tetraphenylporphine:Deformation Effect Due to Bulky N-Substituent Group" Inorganic Chemistry. 32. 1119-1123 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inada et al.: "Structure of Copper(II)Ethylenediamine Complexes in Aqueous and Neat Ethylenediamine Solutions and Solvent-Exchange Kinetics of the Copper(II)Ion in EthylenedIamine As Studied by EXAFS and NMR Methods" Inorganic Chemistry. 32. 3010-3014 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aizawa et al.: "Dissociative Path Promoted by Ion-Pair Formation for Acetonitrile Exchange Reaction of the Palladium(II)Complex with Diethylenetriamine" Chemistry Letters. 1607-1610 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inada et al.: "In-Laboratory Stopped-Flow Extended X-ray Absorption Fine Structure Apparatus in the Dispersive Mode for Determination of the Structure of Short-Lived Intermediates" Review of Scientific Instruments. 65. 18-24 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Ohtaki et al.: "Direct Structural Determination of the Short-Lived Intermediate Formed in Dynamic Processes of the Copper(II)Incorporation into Mercury(II)Porphyrin by the Newly Developed Stopped-Flow EXAFS Method" Journal of the Chemical Society,Chemical Communication. 1023-1025 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inada et al.: "Solvation Structures of Manganese(II),Iron(II),Cobalt(II),Nickel(II),Copper(II),Zinc(II),Cadmium(II),and Indium(III)Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy:Variation of Coordination Number" Inorganic Chemistry. 33. 1875-1880 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aizawa et al.: "Variable-Temperature and Variable-Pressure Sodium-23 NMR Study on Dissociation Reaction of Sodium(I)Cryptates in Ethylenesiamine" Bulletin of the Chemical Society of Japan. 67. 1048-1053 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Kagayama et al.: "Mechanistic Study on the Reaction of L-Ascorbic Acid with Hexacyanometallate(III)of Iron(III),Ruthenium(III),and Osmium(III)Ions in Aqueous Acidic Solution at Elevated Pressures" Inorganic Chemistry. 33. 1881-1885 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Inamo et al.: "Axial Substitution Reaction of Substituted Pyridine on Chloro(5,10,15,20-tetraphenylporphinato)-chromium(III)in Toluene with Special Reference to the Substituent Effect" Bulletin of the Chemical Society of Japan. 67. 1848-1854 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Natsume et al.: "Hydrolysis,Polymerisation,and Structure of Dimethyltin(IV)in Aqueous Solution.Molecular Structure of the Polymer〔(SnMe_2)_2(OH)_3〕ClO_4" Journal of the Chemical Society,Dalton Transaction. 2749-2753 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aizawa et al.: "Iodo-Ligand Substitution of 〔Pd(pp_3)〕^+(pp_3=Tris(2-diphenylphosphinoethyl)phosphine)by Trimethylphosphite.The First Proposition of the Associative Ligand-Substitution Mechanism of Trigonal-Bipyramidal Five-Coordinate Palladium(II)Complex" Chemistry Letters. 2023-2026 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.D.Takagi et al.: "Variable-Pressure Dynamic-NMR Studies:Effects of Paramagnetic Metal Ions on NMR Parameters on Nonexchanging Systems" Canadian Journal of Chemistry. 72. 2188-2192 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kagawa et al.: "Kinetic Study on Complexation of Boric Acid with 4-Isoprophltropolone in Nonaqueous Solvents" Inorganica Chimica Acta. 231. 115-119 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aizawa et al.: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt(II),Iron(II),and Manganese(II)Ions in Ethylenediamine.Kinetic Chelate Effect and Chelate Strain Effect" Inorganic Chemistry. (in press.).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.D.Takagi et al.: "Mechanistic Study of Oxidation Reaction of Hydroquinone,Catechol,and L-Ascorbic Acid by Dicyanobis(1,10-phenanthroline)iron(III)in Dimethyl Sulfoxide" Journal of Molecular Liquids. (in press.).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Funahashi: "Reaction and Activation Volumes for Some Reactions Involving Metal complexes in Solution" Elsevier, 13 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Funahashi: "High Pressure Liquid and Solution,CJMR Vol.13" Elsevier, 16 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Shimizu, K.Taniguchi, Y.Inada, S.Funahashi, Y.Tsuda, Y.Ito, M.Inamo, and M.Tanaka: "Kinetic Studies of the Incorporation of the Zinc (II) Ion into Water Soluble N-Phenyl-Substituted Porphyrins.Deformation Effect on the Metallation Rate" Bull.CHem.Soc.Jpn.65. 771-776 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Soyama (nee Yokoi), M.Ishii, S.Funahashi, and M.Tanaka: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Study on Solvent Exchange at the Tris (ethylenediamine) nickel (II) Ion in Ethylenediamine" Inorg.Chem.31. 536-538 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Funahashi, K.Ishihara, S.Aizawa, T.Sugata, M.Ishii, Y.Inada, and M.Tanaka: "High-Pressure Stopped-Flow Nuclear Magnetic Resonance Apparatus for the Study of Fast Reactions in Solution" Rev.Sci.Instrum.64. 130-134 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aizawa, Y.Tsuda, Y.Ito, K.Hatano, and S.Funahashi: "Synthesis, Structural Characterization, and Metalation of N-o-Tolyl-5,10,15,20-tetraphenylporphine : Deformation Effect Due to Bulky N-Substituent Group" Inorg.Chem.32. 1119-1123 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Inada, K.Ozutsumi, S.Funahashi, S.Soyama, T.Kawashima, and M.Tanaka: "Structure of Copper (II) Ethylenediamine Complexes in Aqueous and Neat Ethylenediamine Solutions and Solvent-Exchange Kinetics of the Copper (II) Ion in Ethylenediamine As Studied by EXAFS and NMR methods" Inorg.Chem.32. 3010-3014 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aizawa, T.Yagyu, and S.Funahashi: "Dissociative Path Promoted by Ion-Pair Formation for Acetonitrile Exchange Reaction of the Palladium (II) Complex with Diethylenetriamine" Chem.Lett.1607-1610 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Inada, S.Funahashi, and H.Ohtaki: "In-Laboratory Stopped-Flow Extended X-Ray Absorption Fine Structure Apparatus in the Dispersive Mode for Determination of the Structure of Short-Lived Intermediates" Rev.Sci.Instrum.65. 18-24 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Ohtaki, Y.Inada, S.Funahashi, M.Tabata, K.Ozutsumi, and K.Nakajima: "Direct Structural Determination of the Short-Lived Intermediate Formed in the Dynamic Incorporation of a Copper (II) Ion into a Mercury (II) Porphyrin by the Stopped -Flow EXAFS Method" J.Chem.Soc., Chem.Commun.1023-1025 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Inada, K.Sugimoto, K.Ozutsumi, and S.Funahashi: "Solvation Structures of Manganese (II), Iron (II), Cobalt (II), Nickel (II), Copper (II), Zinc (II), Cadmium (II), and Indium (III) Ions in 1,1,3,3-Tetramethylurea AS Studied by EXAFS and Electronic Spectroscopy. Variation of Coordination Number" Inorg.Chem.33. 1875-1880 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aizawa and S.Funahashi: "Variable-Temperature and Variable-Pressure Sodium-23 NMR Study on Dissociation Reaction of Sodium (I) Cryptates in Ethylenediamine" Bull.Chem.Soc.Jpn.67. 1048-1053 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Kagayama, M.Sekiguchi, Y.Inada, H.D.Takagi, and S.Funahashi: "Mechanistic Study of the Reaction of L-Ascorbic Acid with Hexacyanometalate (III) Ions of Iron (III), Ruthenium (III), and Osmium (III) in Aqueous Acidic Solution at Elevated Pressures" Inorg.Chem.33. 1881-1885 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Inamo, S.Sugiura, H.Fukuyama, and S.Funahashi: "Axial Substitution Reaction of Substituted Pyridine on Chloro (5,10,15,20-tetraphenyl-porphinato) chromium (III) in Toluene with Special Reference to the Substituent Effect" Bull.Chem.Soc.Jpn.67. 1848-1854 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Natsume, S.Aizawa, K.Hatano, and S.Funahashi: "Hydrolysis, Polymerisation, and Structure of Dimethyltin(IV) in Aqueous Solution. Molecular Structure of the Polymer [(SnMe_2)_2(OH)_3]ClO_4" J.Chem.Soc., Dalton Trans.2749-2753 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aizawa and S.Funahashi: "Iodo-Ligand Substitution of [Pd(pp_3)]^+ (pp_3=Tris (2-diphenylphosphinoethyl) phosphine) by Trimethylphosphite. The First Proposition of the Associative Ligand-Substitution Mechanism of Trigonal-Bipyramidal Five-Coordinate Palladium (II) Complex" Chem.Lett.2023-2026 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.D.Takagi, K.Matsuda, S.Aizawa, S.Funahashi, S.D.Kinrade, and T.W.Swaddle: "Variable-Presure Dynamic-NMR Studies : Effects of Paramagnetic Metal Ions on NMR Parameters in Nonexchanging Systems" Can.J.Chem.72. 2188-2192 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Kagawa, K.Sugimoto, and S.Funahashi: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solvents" Inorg.Chem.Acta. 231. 115-119 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aizawa, K.Matsuda, T.Tajima, M.Maeda, T.Sugata, and S.Funahashi: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt (II), Iron (II), and Manganese (II) Ions in Ethylenediamine. Kinetic Chelate Effect and Chelate Strain Effect" Inorg.Chem.(in press.).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.D.Takagi, N.Kagayama, M.Matsumoto, T.Tarumi, and S.Funahashi: "Mechanistic Study of Oxidation Reaction of Hydroquinone, Catechol, and L-Ascorbic Acid by Dicyanobis (1,10-phenanthroline) iron (III) in Dimethyl Sulfoxide" J.Mol.Liq.(in press.).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1996-04-15  

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