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Chemical Consequences of Assemblage of Transition Metal Ions or Metal Complexes

Research Project

Project/Area Number 01430009
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionTohoku University

Principal Investigator

ITO Tasuku  Tohoku Univ., Fac. of Sci., Dept. of Chem., Prof., 理学部, 教授 (90007328)

Co-Investigator(Kenkyū-buntansha) NAGASAWA Akira  Saitama Univ., Fac. of Sci., Dept. of Chem., Assoc. Prof., 理学部, 助教授 (40108452)
KIDO Hiroaki  Tohoku Univ., Fac. of Sci., Res. Assoc., 理学部, 助手 (40004444)
SASAKI Yoichi  Tohoku Univ., Fac. of Sci., Assoc. Prof., 理学部, 助教授 (30004500)
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥18,500,000 (Direct Cost: ¥18,500,000)
Fiscal Year 1990: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1989: ¥16,000,000 (Direct Cost: ¥16,000,000)
KeywordsPolynuclear Metal Complex / Metal Cluster Complex / ^<99>Ru NMR / Carboxylate Bridged Complex / Macromolecular Complex / Redox Behavior / ^<99>Ru NMR / 金属核 / ニオブ-93ーNMR / 位置選択的反応性 / 多彩な酸化還元挙動
Research Abstract

1. ^<99>Ru NMR of Ru (III) Dimer and Related Compounds. ^<99>Ru NMR spectra have been measured on senen Ru (III) polynuclear complexes, which are essentially diamagnetic through Ru (III)-Ru (III) interaction. Effects of oxidation sate, donor atom, and metal-metal bond upon chemical shift have been studied.
2. Synthesis and Characterization of Carboxylate Bridged Polynuclear Complexes. More than 20 new compounds have been synthesized, and their properties have been studied from the view point of the assemblage effects.
(1) Novel Pt (III) dimers in which CH_2COO^<2-> bridges two Pt's through C and O have been synthesized.
(2) In a pyrazine bridged dimer of the oxo, carboxylato bridged Ru trinuclear cluster, we produced successfully "mixed valence" states between the trinuclear units.
(3) We found that large (20-26) membered Curtis macrocycles (fully saturated form) act as a dinucleating ligand for Cu (II) by taking up two additional small bridging ligands such as OR^-, OH^-, or CH_3COO^-. Such Cu (II) dimers show generally anti-ferromagnetic interaction. The degree of the interaction was found to be very sensitive to the core structure of the dimer.
(4) A new photo-induced ligand substitution was found in oxo, carboxylato bridged trinuclear Ru complexes with the CO terminal ligand.
3. Synthesis of Macromolecular Complexes having Trinuclear Ru Cluster Unit. Six new macromolecular complexes comprised of 4-polyvinylpyridine and oxo, carboxylato bridged Ru trinuclear cluster have been synthesized. Under certain conditions, thin film of the complex coated on a glassy carbon electrode showed reversible redox response in an aqueous solution.

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (29 results)

All Other

All Publications (29 results)

  • [Publications] S.Ikari,Y.Sasaki,and T.Ito: "(μーEthylenediaminetetraacetato)(μーoxo)(μーsulfido)bis(oxotungstate(V)) The First Crystallographically Characterized Complex Containing the W_2(O)_2(μーO)(μーS) Unit." Inorganic Chemistry. 28. 447-451 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Nakada,A.Nagasawa,Y.SaSaki,and T.Ito: "Redox Properties of a Series of Iron(III) Trinuclear Carboxylates,[Fe_3(μーO)(μーRCO_2)_6(L)_3]^<n+>" Chemistry Letters. 753-756 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S.Jin,K.Toriumi,and T.Ito: "Structure of a Linear Chain Chloroーbridged Binuclear Platinum Complex, (NH_4)_4[Pt_2C1(P_2O_5H_2)_4]" Acta Crystallographica. C45. 1415-1416 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Yamaguchi,Y.Sasaki,and T.Ito: "Unusual C,OーBridging Coordination of Acetate and Acetylacetonate Ligands in the Platinum Clusters,[Pt^<III>_2(CH_2COO)_2(CH_3COO)_2Cl_2]^<2-> and Pt^<II>_4(CH_3COO)_4(CH_3COCHCOCHCC3DD)_4." Journal of American Chemical Society. 112. 4038-4040 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K.Nakata,A.Nagasawa,N.Soyama,Y.Sasaki,and T.Ito: "Kinetic Studies on the Terminal Ligand Substitution Reactions of AcetateーBridged Trinuclear Molybdenum and Tungsten Cluster Complexes [Mo_3(CCH_3)(O)(CH_3COO)_6(L)]^+ and [W_3(O)(CH_3COO)_6(H_2O)_3]^<2+>." Inorganic Chemistry. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] D.Akashi,H.Kido,Y.Sasaki,and T.Ito: "Preparation and Electrochemical Response of Poly(4ーvinylpyridine)ー Coordinated Oxoーacetato Triruthenium Cluster Film"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Ikari, Y. Sasaki, and T. Ito: ""(mu-Ethylenediaminetetra-acetate)(mu-oxo)(mu-sulfido)bis(oxotungstate(V)) : The First Crystallographically Characterized Complex Containing the W_2(O)_2(mu-O)(mu-S) Unit"" Irong. Chem.28. 447 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K. Nakata, A. Nagasawa, Y. Sasaki, and T. Ito: ""Redox Properties of a Series of Iron(III) Trinuclear Carboxylates, [Fe_3(mu_3-O(mu-RCO_2)_6(L)_3]^<n+>"" Chem. Left.753. (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Jin, K. Toriumi, and T. Ito: ""Structure of a Linear-Chain Chloro-bridged Binuclear Platinum Complex, (NH_4)_4[Pt_2Cl(P_2O_5H_2)_4]"" Acta Crystallogr.C45. 1415 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S. Ikari, Y. Sasaki, A. Nagasawa, C. Kabuto, and T. Ito: ""A New Mixed Molybdenum-Tungsten Dimer Complex, Bis(mu-oxo)(mu-oxo)(mu-ethylenediaminetetraacetato-N, N')oxomolybdenum(V)-oxotungstate(V)"" Inorg. Chem.28. 1248 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Yamaguchi, Y, Sasaki, and T. Ito: ""Unusual C, O-Bridging Coordination of Acetate and Acetylacetonato Ligands in the Platinum Clusters, [Pt^<III>_2(mu-CH_2COO)_2(mu-CH_3COO)_2Cl_2]^<2-> and Pt^<II>_4(mu-CH_3COO)_4(mu-CH_3COCHCOCH_3)_4"" J. Am. Chem. Soc.112. 4038 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] K. Nakata, A. Nagasawa, N. Soyama, Y. Sasaki, and T. Ito: ""Kinetic Studies on the Terminal Ligand Substitution Reactions of Acetate-Bridged Trinuclear Molybdenum and Tungsten Cluster Complexes, [Mo_3(mu_3-CH_3)(mu-CH_3COO)_6(L)_3]^+ (L=H_2O or pyridine) and [W_3(mu_3-O)-(mu-CH_3COO)_6(H_2O)_3]^<2+>"" Inorg. Chem.30. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Ochi, Y. Sasaki, T. Yamaguchi, and T. Ito: ""Rapid Unidentate-chelate Equilibrium of Acetate Ligands on the Ruthenium-Analog of the Hemerythrin Active Center and the Crystal Structure of [Ru_2(mu-O)(mu-CH_3COO)_2(H_2O)(CH_3OH)(P(C_6H_5)_3)_2] H_2O Having Unidentate Acetates""

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] D. Akashi, H. Kido, Y. Sasaki, and T. Ito: ""Preparation and Electrochemical Response of Poly(4-vinylpyridine)-Coordinated Oxo-acetoro Triruthenium cluster Film""

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Y. Sasaki, M. Suzuki, A. Nagasawa, A. Tokiwa, M. Ebihara, T. Yamaguchi, C. Kabuto, T. Ochi, and T. Ito: ""Preparation, Structure, and Properties of the Bis(mu-acetato)(mu-oxo) Ruthenium (III) Dimers, [Ru_2(mu-O)(mu-CH_3COO)_2(pyridine)_6]^<2+> and [Ru_2(mu-O)(mu-CH_3COO)_2(2, 2'-bipyridine)_2(pyridine)_2]^<2+>""

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] S.Ikari,Y.Sasaki,and T.Ito: "(μーEthylenediaminetetraacetato)(μーoxo)(μーsulfido)bis(oxotungstate(V))The First Crystallographically Characterized Complex Containing the W_2(0)_2(μーO)(μーS) Unit." Inorganic Chemistry. 28. 447-451 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Nakada,A.Nagasawa,Y.Sasaki,and T.Ito: "Redox Properties of a Series of Iron(III) Trinuclear Carboxylates,[Fe_3(μーO)(μーRCO_2)_6(L)_3]^<n+>" Chemistry Letters. 753-756 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Jin,K.Toriumi,and T.Ito: "Structure of a Linear Chain Chloroーbridged Binuclear Platinum Complex,(NH_4)_4[Pt_2Cl(P_2O_5H_2)_4]" Acta Crystallographica. C45. 1415-1416 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Yamaguchi,Y.Sasaki,and T.Ito: "Unusual C,OーBridging Coordination of Acetate and Acetylacetonate Ligands in the Platinum Clusters,[Pt^<III>_2(CH_2COO)_2(CH_3COO)_2Cl_2]^<2-> and Pt^<II>_4(CH_3COO)_4(CH_3COCHCOCH_3)_4." Journal of American Chemical Society. 112. 4038-4040 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] K.Nakata,A.Nagasawa,N.Soyama,Y.Sasaki,and T.Ito: "Kinetic Studies on the Terminal Ligand Substitution Reactions of AcetateーBridged Trinuclear Molybdenum and Tungsten Cluster Complexes [Mo_3(CCH_3)(O)(CH_3COO)_6(L)]^+ and [W_3(O)(CH_3COO)_6(H_2O)_3]^<2+>." Inorganic Chemistry. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] D.Akashi,H.Kido,Y.Sasaki,and T.Ito: "Preparation and Electrochemical Response of Poly(4ーvinylpyridine)ーCoordinated Oxoーacetato Triruthenium Cluster Film"

    • Related Report
      1990 Annual Research Report
  • [Publications] S.Ikari: "(muーEthylenediaminetetraacetato)(muーoxo)(muーsulfido)bis(oxotungstate(V):The First Crystallographically Characterized Complex Containing the W_2(O)_2(muーO)(muーS)Unit" Inorganic Chemistry. 28. 447-451 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Nakata: "Redox Properties of a Series of Iron(III)Trinuclear Carboxylates,[Fe_3(mu_3ーO)(muーRCO_2)_6(L)_3]^<n+>" Chemistry Letters. 753-756 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] S.Ikari: "A New Mixed MolybdenumーTungsten Dinuclear Complex,Bis(muーoxo)(muーethylenediaminetetraacetatoーN,N')oxomolybdenum(V)oxotungstate(V)" Inorganic Chemistry. 28. 1248-1254 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] S.Jin: "Structure of a LinearーChain ChloroーBridged Binuclear Platinum Complex,(NH_4)_4[Pt_2Cl(P_2O_5H_2)_4]" Acta Crystallographica. c45. 1415-1417 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Yamaguchi: "Facile Regioselective Ligand Substitution for the InーPlane Bridging Acetates in Octakis(muーacetatoーO,O')tetraplatinum(II)" Inorganic Chemistry. 28. 4311-4312 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] S.Ikari: "Asymmetric Distortion of bis(muーoxo)bis(oxotungstate(V))Complexes.Crystal Structure of Bis(muーoxo)(muーN,N'ー(R)ーpropylenediaminetetaacetato)bis(oxotungstate(V))" Inorganic Chemistry. 29. 53-56 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Yamaguchi: "Unusual C,OーBridging Coordination of Acetate and Acetylacetonate Ligands in the Platinum Clusters,[Pt^<III>_2(muーCH_2COOーC,O)_2(muーCH_3COOーO,O')_2Cl_2]^<2-> and Pt^<II>_4(muーCH_3COOーO,O')_4(muーCH_3COCHCOCH_3ーO,C^3)_4." Journal of The American Chemical Society.

    • Related Report
      1989 Annual Research Report
  • [Publications] Y.Sasaki: "Mixed Chromium(III)ーRuthenium(III)Trinuclear Complex,[CrRu_2(muーO)(muーCH_3COO)_6(pyridine)_3]^+" Chemistry Letters.

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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