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THERMODYNAMIC SND KINETIC STUDY ON SOLVATION STERIC INTERACTIONS

Research Project

Project/Area Number 06453051
Research Category

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

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

ISHIGURO Shinichi  KYUSHU UNIVERSITY,FACULTY OF SCIENCE,PROFESSOR, 理学部, 教授 (80111673)

Co-Investigator(Kenkyū-buntansha) MIYAJIMA Toru  KYUSHU UNIVERSITY,FACULTY OF SCIENCE,ASSOCIATE PROFESSOR, 理学部, 助教授 (40128103)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 1995: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1994: ¥5,500,000 (Direct Cost: ¥5,500,000)
KeywordsSOLVATION STERIC EFFECT / SOLVATION STRUCTURE / COMPLEXATION THERMODYNAMICS / COMPLEXATION KINETICS / APROTIC DONOR SOLVENTS / INTERLIGAND INTERACTION / 三元錯体 / 非水溶液反応 / ジメチルホルムアミド / 速度論
Research Abstract

Metal ions exist as solvated complexes in aprotic donor solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), and hexamethylphosphoric triamide (HMPA). The coordination structure and intramolecular interactions of the solvated metal complexes are largely different from those of hydrated metal complexes, and the difference play a key role in thermodynamic and kinetic complexation aspects in these aprotic solvents. In the present study, we particularly focused our attention on solvation steric effects in some aprotic donor solvents. As kinetic aspects on metal complexation in nonaqueous solution have not been revealed yet, we newly introduced a stopped-flow spectrophotometer, and kinetic analyzes have been carried out for the Ni-Cl-bpy systems for which precise thermodynamic analyzes have been accomplished.
It is found that in DMF the rate of formation of the tris-bipyridine nickel (II) complex is reduced when chloride ions coexist in solution. In the Ni-Cl-bpy ternary system … More , the [NiCl (bpy)_2]^+ and [NiCl_2bpy_2] complexes are significantly formed and the pass through these complexes was found to be slow compared to the pass through [NiCl (bpy)_2]^<2+>, suggesting a presence of a specific interaction within the intermediate [NiCl (bpy)_3]^+, in which one bpy coordinates as monodentate. Solvation steric effect exhibited a strong relationship to the ionic radius of metal ions. Halogeno complexation of beryllium, aluminum, cadmium and manganese ions were examined in DMF and DMA,and their thermodynamic parameters were compared. The four-coordinated small beryllium ion show no appreciable steric effect. One the other hand, relatively large and six-coordinated cadmium ion exhibits a significant steric effect. Even larger lanthanide ions show also significant steric efffect, and it is indicated by EXAFS that the coordination number in DMA is reduced by one compared with that in DMF.It is also indicated by ^<89>Y NMR that in DMF-DMA mixtures, the coordination number reduced gradually with increasing DMA content. Less

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] H. Yokoyama: "X-Ray Diffraction Study of Solvation Structure of Cobalt (II) Ion in N, N-Dimethylformamide with Isostructural Substitution Method." Z. Naturforsch,. 50a. 301-306 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] A. Odani: "Calorimetric and ^<195>Pt NMR Studies on Aromatic Ring Stacking between Nucleotides and Platinum DNA Intercalators." Bull. Chem. Soc. Jpn.68. 2093-2102 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Koide: "Solvation and Complexation Equilibria of the Nickel (II) Thiocyanato Complexes in N, N-Dimethylacetamide." J. Chem. Soc. Faraday Trans.91. 2313-2317 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Koide: "Steric Solvent Effect on Small and Large Cations : Calorimetric Study of Halogeno and Thiocyanato Complexes of Beryllium (II) and Cadmium (II) in N, N-Dimethylacetamide," J. Chem. Soc. Faraday Trans.91. 3851-3857 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S. Ishiguro: "Steric Solvent Effect on Formation Thermodynamics and Structure of Halogeno Complexes of Lanthanide (III) Ions in N, N-Dimethylacetamide" J. Chem. Soc. Faraday Trans.92(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Koide: "Solution Equilibria of Zinc (II) and Cadmium (II) Complexes with 2,2'-Bipyridine in N, N-Dimethylacetamide" Solution Chem.24(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Ishiguro: "Steric Effect on Solvation and Complexation of Metal Ions in Solution" Pure & Appl.Chem. 66. 393-398 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Suzuki: "Solution Equilibria of Binary and Ternary Zinc (II) Halogeno Complexes in N,N-Dimethylacetamide" Bull.Chem.Soc.Jpn. 67. 1320-1326 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Steric Interaction of Solvation and Sterically Enhanced Halogeno Complexation of Manganese (II), Cobalt (II) and Nickel (II) Ions in N,N-Dimethylacetamide" Solution Chem.23. 1257-1270 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Ozutsumi: "Solvation Structure of Manganese (II), Iron (II), Cobalt (II), Nickel (II), Copper (II), and Zinc (II) Ions in Hexamethylphosphoric Triamide." J.Phys.Chem.98. 9894-9899 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Molar Enthalpy of Transfer of Divalent Transition Metal Ions and Their Chloro Complexes from N,N-Dimethylformamide to N,N-Dimethylacetamide." J.Solution Chem.24. 511-522 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Thermodynamics and Structure of Isothiocyanato Complexes of Manganese (II), Cobalt (II) and Zinc (II) Ions in N,N-Dimethylacetamide." Z.Naturforsch.50a. 11-17 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Yokoyama: "X-Ray Diffraction Study of Solvation Structure of Cobalt (II) Ion in N,N-Dimethylformamide with Isostructural Substitution Method." Z.Naturforsch.50a. 301-306 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] A.Odani: "Calorimetric and ^<195>Pt NMR Studies in Aromatic Ring Stacking between Nucleotides and Platinum DNA Intercalators." Bull.Chem.Soc.Jpn.68. 2093-2102 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Solvation and Complexation Equilibria of the Nickel (II) Thiocyanato Complexes in N,N-Dimethylacetamide." J.Chem.Soc.Faraday Trans.91. 2313-2317 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Steric Solvent Effect on Small and Large Cations : Calorimetric Study of Halogeno and Thiocyanato Complexes of Beryllium (II) and Cadmium (II) in N,N-Dimethylacetamide." J.Chem.Soc.Faraday Trans.91. 3851-3857 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Ishiguro: "Nonaqueous Solution Chemistry of Lanthanide (III) Ions." Rare Earths. 27. 61-77 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Ishiguro: "Steric Solvent Effect on Formation Thermodynamics and Structure of Halogeno Complexes of Lanthanide (III) Ions in N,N-Dimethylacetamide" J.Chem.Soc.Faraday Trans.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Koide: "Solution Equilibria of Zinc (II) and Cadmium (II) Complexes with 2,2'-Bipyridine in N,N-Dimethylacetamide" J.Solution Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H. Yokoyama: "X-Ray Diffraction Study of Solvation Structure of Cobalt(II) lon in N, N-Dimethylformamide with lsostructural Substitution Method." Z. Naturforsch,. 50a. 301-306 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A. Odani: "Calorimetric and ^<195>Pt NMR Studies on Aromatic Ring Stacking between Nucleotides and Platinum DNA lntercalators." Bull. Chem. Soc. Jpn.68. 2093-2102 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Koide: "Solvation and complexation Equilibria of the Nickel(II) Thiocyanato Complexes in N,N-Dimethylacetamide." J. Chem. Soc. Faraday Trans.91. 2313-2317 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Koide: "Steric Solvent Effect on Small and Large Cations: Calorimetric Stydy of Halogeno and Thiocyanato Complexes of Beryllium(II) and Cadmium(II) in N, N-Dimethylacetamide," J. Chem. Soc. Faraday Trans.91. 3851-3857 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S. Ishiguro: "Steric Solvent Effect on Formation Thermodynamics and Structure of Halogeno Complexes of Lanthanide(III)lons in N, N-Dimethylacetamide" J. Chem. Soc. Faraday Trans.92(in press). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Koide: "Solution Equilibria of Zinc(II) and Cadmium(II) Complexes with 2,2′-Bipyridine in N, N-Dimethylacetamide" Solution Chem.24(in press). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Ishiguro: "Steric effect on solvation and complexation of metal ions in solution" Pure&Appl.Chem.65. 393-398 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Suzuki,M.Koide,S.Ishiguro: "Solutionequilibria of binary and ternary zinc(II)halogeno complexes in N,N-dimethylacetamide" Bull,Chem.Soc.Jpn.67. 1320-1326 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Ozutsumi,Y.Abe,R.Takahashi,S.Ishiguro: "Chloro and bromo complexation of the Mn(II)ion and solvation structure of Mn(II),Co(II),Mi(II),Cu(II)and Zn(II)in HMPA" J.Phys.Chem.98. 9894-9899 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Koide,H.Suzuki,S.Ishiguro: "Steric interaction of solvation and sterically enhanced halogeno complexation of Mn(II),Co(II)and Ni(II)ions in DMA" J.Solution Chem.23. 1257-1270 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Koide,S.Ishiguro: "Molar enethalpies of transfer of some divalent transition metal ions and their chloro complexes from DMF to DMA" J.Solution Chem.24(in press). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Koide,S.Ishiguro: "Thermodynamics and structure of isothiocyanato complexes of Mn(II),Co(II)and Zn(II)in DMA" Z.Naturforsch.50a(in press). (1995)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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