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Development of New Field of Solution Coordination Chemistry from a Viewpoint of Precursor Phenomena for "Supramolecular Effect

Research Project

Project/Area Number 07304045
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

KAIZAKI Sumio  Osaka Univ.Grad.School Sci., Prof., 大学院・理学研究科, 教授 (20089874)

Co-Investigator(Kenkyū-buntansha) ISHIHARA Koji  Waseda Univ., School Sci.Eng., Prof., 理工学部, 教授 (20168248)
SAWADA Kiyoshi  Niigata Univ., Fac.Sci., Prof., 理学部, 教授 (40089850)
ISHIGURO Shinichi  Kyusyu Univ. Fac.Sci., Prof., 理学部, 教授 (80111673)
IIDA Masayasu  Nara Women's Univ.Fac.Sci., Prof., 理学部, 教授 (00107343)
FUNAHASHI Shigenobu  Nagoya Univ.Grad.School Sci., Prof., 大学院・理学研究科, 教授 (30022700)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥9,900,000 (Direct Cost: ¥9,900,000)
Fiscal Year 1997: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1996: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1995: ¥4,200,000 (Direct Cost: ¥4,200,000)
KeywordsCompensation Effect / Micelles / FT Raman Spectroscopy / ^2HNMR / Solution Dynmics / Solvent-Ion Cooperative Interaction / Hydrophobic Ion Association / 超分子効果 / メゾスコピック / ミセル系 / 溶媒和構造 / 配位子置換反応 / 酸化還元反応
Research Abstract

1. For redox reaction rates between dinuclear complexes [VO(sakenO)]_2(CH_2)_n(n=3,6,10,12) and Fe(III), the activation enthalpy and entropy increases with increasing n, and the complimentary effect is observed in this system.
2. The reduction potentials from oxo-bridged Ru(III) dinuclear complexes to (III,II) and (II,II) in acetonitrile are found to shift to positive (ca.1V) by addition of proton donor or BF3, and this shift and the numbers of electrons concerned are controlled by the pKa values of the proton donors.
3. The examination of the interaction of [M(en)_3]^<3+>, [M(chxn)_3]^<3+>, [M(phen)_3]^3(M=Co^<III>, Cr^<III>) with the micelles in terms of ^<59>Co NMR(Co^<III>) and ^<13>C paramagnetic relaxation (Cr^<III>) demonstrates that the extent of the interactions with sulphonic or sulfate ions and carboxylates reflects the selectivity.
4. The possibility and limitation of application for FT Raman spectroscopy to solution coordination chemistry was discussed. The dynamics of chelate ring conformation in solution state was investigated with respect to the solvent effect and temperature dependence by ^2H NMR spectra of paramagnetic Cr(III) complexes. These subjects were discussed in relation with weak interactions in the second coordination sphere.
5. The cooperative interaction between solvents and ions in highly concentrated electrolytes and hydrophobic ion association in aqueous solutions were investigated together with the complex formation in micelles. These studies will be expected to progress in connection with the mesoscopic phenomena.

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (39 results)

All Other

All Publications (39 results)

  • [Publications] T.Fujihara: "Base Hydrolysis in Homometallic Dinuclear Chromium(III)Complexes Bridged by Hydroxide and Carboxylate." J.Chem.Soc.,Dalton Trans.1995. 1823-1831 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Sawada: "Partition and dimerization of ion-pair of tetraalkyl-ammonium salts in xylene." J.Chem.Soc.,Faraday Trans.91. 643-647 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Kondo: "Kinetic Study of the Reaction of Tetramethyl-platinum(IV)Complexes with Acids." Inorg.Chim.Acta. 241. 81-85 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Aizawa: "Complexation Equilibria and Structures of Dimethyltin(IV)Complexes with N-Methyliminodiacetate,…" Inorg.Chim.Acta. 248. 215-224 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Kanamori: "Reduction of Vanadium(IV)to Vanadium(III)by Cysteine Methyl Ester in Water in the Presence of …" Chem.Lett.1997. 423-424 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Kono: "An"B NMR Study of the Kinetics of Methylboronicacid-methylboronate Interchange in Aqueous Solution." Inorg.Chim.Acta. 262. 91-96 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takashi Fujihara, Yuriko Abe and Sumio Kaizaki: "Base Hydrolysis in Homometallic Dinuclear Chromium(III) Complexes Bridged by Hydroxide and Carboxylate." J.Chem.Soc., Dalton Trans.1995. 1823-1831

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Sawada, T.Sohara, and Y.Kikuchi: "Partition and dimerization of ion-pair of tetraalkylammonium salts in xylene." J.Chem.Soc., Faraday Trans.91. 643-647 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yuichi Kondo, Minako Ishikawa, and Koji Ishihara: "Kinetic Study of the Reaction of Tetramethylplatinum(IV) Complexes with Acids." Inorg.Chim.Acta. 241. 81-85 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Aizawa, T.Natsume, K.Hatano, and S.Funahashi: "Complexation Equilibria and Structures of Dimethyltin(IV) Complexes with N-Methyliminodiacetate, Pyridine-2,6-dicarboxylate, Ethylenediamine-N,N'-diacetate, and Ethylenediamine-N,N,N', N'-tetraacetate." Inorg.Chim.Acta. 248. 215-224 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Kanamori, Y.Kinebuchi, and H.Michibata: "Reduction of Vanadium(IV) to Vanadium(III) by Cysteine Methyl Ester in Water in the Presence of Amino Polycarboxylates." Chem.Lett.1997. 423-424

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Yoko Kono, Koji Ishihara, Akira Nagasawa, Kimiko Umemoto, and Kuzuo Saito: "An ^<11>B NMR Study of the Kinetics of Methylboronic acid-methylboronate Interchange in Aqueous Solution." Inorg.Chim.Acta. 262. 91-96 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Inada: "Laboratory Stopped-Flow XAFS Apparatus. Structure Determination of the Short-Lived Peroxochromium・・・・" Z.Naturforsch.52b. 711-718 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Umebayashi: "Unusual Behaviour of Thiocyanato Complexation with Copper(II) and Zinc(II) Ions in Miceller Solutions of a・・・・" J.Chem.Soc.,Faraday Trans.93 (7). 1377-1381 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Sawada: "Electronic Spectra of Ion Pairs of Picrate Ion with Alkali-metal Polyether Complexes in Non-agueous・・・・" J.Chem.Soc.,Faraday Trans.93 (10). 1903-1908 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Sasaki: "Reactivity of di- and tri-nuclear complexes of heavy mid-transition elements : A case of oxo-carboxylato・・・・" Pure & Appl.Chem.69 (1). 205-210 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ozutsumi: "Structural Studies on Preferential Solvation of Silver(1) Ion by Acetonifrile over N,N-Dimethyl・・・・・" J.Molecular Liquids. 73,74. 385-396 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Yokoyama: "Hydrophobic Hydration Structures of Tris (1,10-phenanthroline) metal and Tris (2,2'-bipyridine) metal・・・" Bull.Chem.Soc.Jpn.70. 2357-2367 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Narumi Sakagami: "Syntheses and Characterization of Diamine-N,N′-dicarboxylato Chromate(III) Dinuclear Complexes Bridged by Pyrazole-3,5-dicarboxylate." Inorg.Chem.35. 683-688 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Auzawa: "Nitrogen-14 NMR Study on Solrent Exchange of Octahedral Cobalt(II) Ion in Neat1,3-Propanediamine and n-Propylamine……" Inorg.Chem.35. 1338-1342 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Kan Kanamori: "Heptacoordinate Vanadium(III)Complexes Containing a Didentate Sultate Ligand." Bull.Chem.Soc.Jpn.69. 2901-2909 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Sugimoto: "Preparation,Structure,and Properties of Bls(μ-oxo)dirhenium(III,IV)and-dirhenium(IV)Complexes of Tris(2-pyridylmethy1)amine……" Inorg.Chem.35. 7092-7088 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Itoh: "Thermodynamic and Kinetic Studies of Zinc(II)-Triamine Complexes as Models of CA and AP." Bull.Chem.Soc.Jpn.69. 1265-1274 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Sawada: "Eight-membered Chelate Ring Complexes of Cobalt(III)-polyamine Complexes of Aminopolyphosphonates in Aqueous Solution" J.Chem.Soc.Dalton Trans.1996. 3077-3085 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yukiko Terasaki: "Solvent-dependent ^2H NMR spectra and solvatochromism in liagnd field absorption bands of cis-[CrF_2N_4]type complexes with trimethylenetetramine pyridine and 22′-bipyridine" J.Chem.Soc.Dalton Trans.1995. 2837-2841 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa: "Variable-Temperature and-Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt(ll),Iron(ll)、and Manganese(ll)lons in Ethylenediamine.Kinetic Chelate Effect and Chelate Strain Effect" Inorg.Chem.34. 2042-2047 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Iida: "^<59>Co NMR Spectroscopic Chiral Discrimination of[Co(en)_3]^<3t> Enantiomers in Ionic Interacting Systems" Bull.Chem.Soc.Jpn.68. 1337-1344 (1995)

    • Related Report
      1995 Annual Research Report
  • [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)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Sawada: "Ion-pair of tetraalkylammonium picrate" J.Mol.Liquids. 65/66. 266-268 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Takashi Fujihara: "Base Hydrolysis in Homometallic Dinuclear Chromium(lll) Complexes Bridged by Hydroxide and Carboxyrate" J.Chem.Soc.Dalton Trans.1995. 1823-1831 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yuichi Kondo: "Kinetic Study of the Reaction of Tetramethylplatinum(IV)Complexes with Acids" Ionrg.Chim.Acta. 241. 81-85 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akihiro Kikuchi: "Redox Behaviour of the Oxo-bridged Diruthebnium Complex,[Ru_2(μ-O)(μ-MeCO_2)_2(bpy)_2(mim)_2]^<2+>in Acetonitrile in the Presence of Various Proton Donors(bpy=2,2′-bipyridine,mim=1-methylimidazole)" J.Chem.Soc.,Chem.Commun.1995. 2125-2126 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Masaaki Tabata: "Kinetics and Mechanism of Metal-Substitution Reaction of Homodinuclear Mercury(ll) Porphyrin with Zinc(ll) with Particular Reference to a Heterodinuclear Metalloporphyrin Intermediate" Inog.Chem.34. 6492-6496 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] E.Iwamoto: "Cooperative interactions between ions and water in the chloride ion and water coordination to a square-planar nickel complex ion in concentrated aqueous solutions" J.Chem.Soc.Faraday Trans.91. 627-630 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Ozutsumi: "Structure of the Monohalogenocadmium(ll) Complexes in N,N-Dimethylformamide" J.Mol.Liquids,. 65/66. 361-364 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Haruhiko Yokoyama: "X-Ray Diftraction Study of Solvation Structure of the Cobalt(ll) lon in N,N-Dimethylformamide Solution" Z.Naturforsch.50a. 301-306 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] F.MD.Akhter: "Photochemical Desulfurization of a Sulfinate-S-Cobalt(lll) Complex.Formation of an Organic Peroxide Complex" Chem.Lett.1996. 81-82 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Iida: "Appreciable Effects of lon-Pairing on the ^<59>Co Electric Field Gradients in the NMR Relaxations of[Co(chxn)_3]^<3+>" J.Phys.Chem.99. 4347-4352 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kan Kanamori: "Syntheses,Characterization,and Properties of Vanadium(lll) Complexes Containing Tripodal Tetradentate Ligands with Single Pyridy Groups" Bull.Chem.Soc.Jpn.68. 2581-2589 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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