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A Study on Structure and Spin Equilibria of Metal Complexes in Solution.

Research Project

Project/Area Number 02640469
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionTokyo Institute of Technology at Nagatsuta

Principal Investigator

ISHIGURO Shin-ichi  Tokyo Institute of Technology at Nagatsuta, 大学院・総合理工学研究科, 助教授 (80111673)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsMetal Complexes / Complexation / Calorimetry / Spectrophotometry / Organic Solvents / Temperature dependence / Equilibrium isomers / Thermodynamic parameters
Research Abstract

Bivalent transition metal ions form a series of mononuclear complexes with halide ions in aprotic donor solvents. These metal ions are usually six-coordinated with solvent molecules and the coordination structure around a metal ion changes to four-coordination upon complexation with halide ions. It is suggested that a halogeno complex consists of two equilibrium species with different numbers of coordinating solvent molecules. The equilibrium may change with temperature. Thus, in this work, we investigated temperature dependence of themodynamic parameters of complexation and electronic spectra of individual complexes by using a precise titration calorimetry system and spectrophotometric titration system developed in our laboratory.
In dimethylacetamide (DMA), the reaction enthalpy and entropy values of chloro complexation of the nickel (II) ion show remarkable temperature dependence. The result is consistent with that from electronic spectra, suggesting that the monochloro complex consists of [Nicl(DMA)_5]^+ and [NiCl(DMA)_4]^+, and the dichloro complex [NiCl_2(DMA)_3] and [NiCl_2(DMA)_2]. The reaction enthalpy and entropy values of halogeno complexation of the zinc (II) ion suggested that the number of coordinating solvent molecules in the metal solvate ion is less than six, implying that [Zn(DMA)_6]^<2+> and [Zn(DMA)_4]^<2+> are present in DMA. In fact, an EXAFS spectroscopy shows the average coordination number of 4.6.
The adduct formation reaction between [Ni(dtp)_2] (dtp = dithiophosphate (C_2H_5)O_2PS_2) with various nitrogen-donor ligands have been thermodynamically and spectrophotometrically studied, because its electronic state changes from low spin to high spin upon complexation.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Ryouta Takahashi Shin-ichi Ishiguro: "Inner-spere and Outer-sphere Complexes of Yttrium(III),Lanthanum(III),Neodymium(III),Terbium(III) and Thulium(III) with Halide Ions in DMF" J.Chem.Soc.Faraday Trans.87. 3379-3383 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Yuriko Abe Shin-ichi Ishiguro: "Thermodynamics of Complexation of Zinc(II) with Chloride,Bromide and Iodide Ions in Hexamethylphosphoric Triamide" J.Solution Chem.20. 793-803 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Shin-ichi Ishiguro Ryouta Takahashi: "Thermodynamics of Chloro Complexation of Lanthanide(III) Ions in N,N-dimethylformamide" Inorg.Chem.30. 1854-1858 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Shin-ichi Ishiguro Makoto Miyauchi Kazuhiko Ozutumi: "Thermodynamics of Formation of Binary and Ternary Complexes of Zinc(II) with Halide and Thiocyanate Ions and 2,2'-Bipyridine in Dimethylformamide" J.Chem.Soc.Dalton Trans.2035-2041 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S.Ishiguro,H.Suzuki X-Z.You,Y-P.Yu K.Saito: "Thermodynamics of adduct formation of Ni(dtp)_2 (dtp = (C_2H_5O)_2PS_2) with some-nitrogen-donor bases in benzene" Inorg.Chim.Acta. 180. 111-115 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Shin-ichi Ishiguro Kazuhiko Ozutsumi: "Thermodynamics and Structure of Isothiocyanato Complexes of Manganess(II),Cobalt(II),and Nickel(II) Ions in N,N-Dimethylformamide" Inorg.Chem.29. 1117-1123 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] R. Takahashi, S. Ishiguro: "Inner-sphere and outer-sphere complexes of Yttrium (III), Neodymium (III), Terbium (III) and Thulium (III) with halide ions in DMF" J. Chem. Soc. Faraday Trans.87. 3379-3383 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Abe and S. Ishiguro: "Thermodynamics of complexation of zine (II) with chloride, bromide and iodide ions in hexamethylphosphoric triamide" J. Solution Chem.20. 793-803 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S. Ishiguro and R. Takahashi: "Thermodynamics of chloro complexation of lanthanide (III) ions in N, N-dimethylformamide" Inorg. Chem.30. 1854-1858

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S. Ishiguro, M. Miyauchi, K. Ozutsumi: "Thermodynamics of formation of binary and ternary complexes of zinc (II) with halide and thiocyanate ions and 2, 2'-bipyridine in dimethylformamide" J. Chem. Soc. Dalton Trans.2035-2041 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S. Ishiguro, H. Suzuki, X-Z. You, Y-P. Yu, K. Saito: "Thermodynamics of adduct formation of Ni (dtp)_2 (dtp = (C_2H_5O)_2PS_2) with some-nitrogen-donor bases in benzene" Inorg. Chim. Acta. 180. 111-115 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] S. Ishiguro and K. Ozutsumi: "Thermodynamics and structure of isothiocyanato complexes of manganese (II), cobalt (II) and nickel (II) ions in N, N-dimethylformamide" Inorg. Chem.29. 1117-1123 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Ryouta Takahashi,Shinーichi Ishiguro: "Innerーspere and Outerーsphere Complexes of Yttrium(III),Lanthanum(III),Neodymium(III),Terbium(III)and Thulium(III)with Halide Ions in DMF" J.Chem.Soc.Faraday Trans.87. 3379-3383 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Yuriko Abe,Shinーichi Ishiguro: "Rhermodynamics of Complexation of Zinc(II)with Chloride,Bromide and Iodide Ions in Hexamethylphosphoric Triamide" J.Solution Chem.20. 793-803 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Tyouta Rakahashi: "Thermodynamics of Chloro Complexation of Lanthanide(III)Ions in N,Nーdimethylformamide" Inorg.Chem.30. 1854-1858 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Makoto Miyauchi,Kazuhiko Ozutumi: "Thermodynamics of Formation of Binary and Ternary Complexーes of Zinc(II)with Halide and Thiocyanate Ions and 2,2^,ーBipyridine in Dimethylformamide." J.Chem.Soc.Dalton Trans.2035-2041 (1990)

    • Related Report
      1991 Annual Research Report
  • [Publications] S.Ishiguro,H.Suzuki,XーZ.You,YーP.Yu,K.Saito: "Thermodynamics of adduct Formation of Ni(dtp)_2(dtp=(C_2H_5O)_2PS_2)with someーnitrogenーdonor bases in benzene" Inorg,Chim.Acta. 180. 111-115 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Kazuhiko Ozutsumi: "Thermodynamics and Structure of Isothiocyanato Complexes of Manganese(II),Cobalt(II),and NiCkel(II)Ions in N,NーDimethylformamide" Inorg,Chem.29. 1117-1123 (1990)

    • Related Report
      1991 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Kazuhiko Ozutsumi: "Thermodynamics and Structure of Isothiocyanato Complexes of Manganese(II),Cobalt(II)and Nickel(II)Ions in N,NーDimethylformamide" Inorganic Chemistry. 29. 1117-1123 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Honoh Suzuki,Shinーichi Ishiguro,Hitoshi Ohtaki: "Formation of Chloro Complexes of Manganese(II),Cobalt(II),Nickel(II)and Zinc(II)in Dimethyl Sulphoxide" J.Chem.Soc.Faraday Trans.86. 2179-2185 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Makoto Miyauchi,Kazuhiko Ozutsumi: "Thermodynamics of Formation of Binary and Ternary Complexes of Zinc(II)with Halide and Thiocyanate Ions and 2,2'ーBipyridine in Dimethylformamide" J.Chem.Soc.Dalton Trans.2035-2041 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Honoh Suzuki,Kazuo Saito: "Thermodynamics of adduct formation of Ni(dtp)_2(dtp=(C_2H_5O)_2PS_2)with some nitrogenーdonor bases in benzene" Inorganica Chimica Acta.

    • Related Report
      1990 Annual Research Report
  • [Publications] Shinーichi Ishiguro,Ryouta Takahashi: "Thermodynamics of Chloro Complexation of Lanthanide Ln(III)Ions in N,NーDimethylformamide" Inorganic Chemistry.

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Ozutsumi,K.Thoji,Y.Udagawa,S.Ishiguro: "Structure of Cobalt(II)Ion and Triーand Tetrachloro cobaltate(II)Complexes in N,NーDimethylformamide Determined by the Fluorescent EXAFS Method" Bull.Chem.Soc.Jpn.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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