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1995 Fiscal Year Final Research Report Summary

Low temperature liquid-phase synthesis and properties of solid state metal sulfides which are unstable at high temperatures

Research Project

Project/Area Number 06403009
Research Category

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

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

SAITO Taro  The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (90011006)

Co-Investigator(Kenkyū-buntansha) IMOTO Hido  The University of Tokyo, Graduate Schoool of Science, Ass.Prof., 大学院・理学系研究科, 助教授 (20168529)
KOBAYASHI Akiko  The University of Tokyo, Graduate School of Science, Ass.Prof., 大学院・理学系研究科, 助教授 (50011705)
Project Period (FY) 1994 – 1995
KeywordsCluster complex / Chromium / Triethylphosphine / Chevrel phase / Mixed valence / Raft cluster / Isoelectronic analogy
Research Abstract

Treatment of a hexanuclear cluster complex [Cr_6S_8 (PEt_3) _6] with S_8 in toluene at refluxing temperatures has formed a dodecanuclear cluster complex [Cr_<12>S_<16> (PEt_3) _<10>] by abstraction of one triethylphosphine from each cluster. The dimeric cluster has a mu_4-S---->Cr and a weak Cr-Cr bonds between the cluster units, which are similar to those in the Chevrel phase compunds. The expansion of the mixed valency state of the cluster has been demonstrated in the cyclic voltammetry and magnetic measurements on the cluster complexes. Thus the dimerization can be regarded as the first step to prepare "chromium Chevrel compunds" by low temperature polymerization of molecular clusters.
Another novel dimerization of trinuclear molybdenum cluster complexes to form [Mo_6E_8Cl_6- (PEt_3) _6l (E=S,Se) has been found. The number of the cluster valence electrons in the raft-type clusters and the tetranuclear cluster complexes prepared in this study corresponds well to the number of pi-electrons in fused aromatic compounds. The meaning of this "Isoelectronic Analogy" is being studied.

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] H.Imoto: "Molecular Orbital Calculations of Octahedral Molybenum Cluster Complexes with the DV-Xα Method" Inorg.Chem.,. 34. 2415-2422 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tsuge: "Synthesis,Structure,and Molecular Orbital Calculation of the Bicappe Triangular Molybdenum Cluster Complex[Mo_3S_5(PMe_3)_6]" Inorg.Chem.,. 34. 3404-3409 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Mizutani: "Synthesis and Structure of a Seven Electron Triangular Cluster Complex [Mo_3S_4Cl_3(dppe)_2(PEt_3)]" J.Cluster Sci.,. 6. 523-532 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Mizutani: "Syntheses and Structures of Raft-type Hexanuclear Molybdenum Chloro Chalcogenide Cluster Complexes[Mo_6E_8Cl_6(PEt_3)_6](E=S,Se)" Inorg.Chem.,. 35. 244-247 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tsuge: "Synthesis and Structure of Tetranuclear Cluster Complexes of Molybdenum [Mo_4(μ_3-S)_2(μ_2-S)_4X_2(PMe_3)_6]X=SH,Cl,Br,I,SCN)and[Mo_4(μ_3-S)_2-(μ_2-S)_4(dtc)_2(PMe_3)_4]" J.Cluster Sci.,. 7(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tsuge: "Syntheses,Structures,and Molecular-Orbital Calculations of Chromium Chevrel-Type Cluster Complexes[Cr_6E_8(PR_3)_6](E=S,PR_3=PEt_3,PMe_3;E=Se,PR_3=PEt_3,PMe_3,PMe_2Ph)" Bull.Chem.Soc.Jpn.,. 69(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Taro Saito(M.H.Chisholm ed.): "Early Transition Metal Clusters with π-Donor Ligands" VCH, 101 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Imoto, T.Saito, and H.Adachi: "Molecular Orbital Calculations of Octahedral Molybdenum Cluster Complexes with the DV-Xalpha Method" Inorg.Chem.34. 2415-2422 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tsuge, H.Imoto, and T.Saito: "Synthesis, Structure, and Molecular Orbital Calculation of the Bicapped Triangular Molybdenum Cluster Complex [Mo_3S_5 (PMe_3) _6]" Inorg.Chem.34. 3404-3409 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Mizutani, H.Imoto, and T.Saito: "Synthesis and Structure of a Seven Electron Triangular Cluster Complex [Mo_3S_4Cl_3 (dppe) _2 (PEt_3)]" J.Cluster Sci.6. 523-532 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Mizutani, S.Yamada, H.Imoto, and T.Saito: "Syntheses and Structures of Raft-type Hexanuclear Molybdenum Chloro Chalcogenide Cluster Complexes [Mo_6E_8Cl_6 (PEt_3) _6] (E=S,Se)" Inorg.Chem.35. 244-247 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tsuge, S.Mita, H.Fujita, H.Imoto, and T.Saito: "Synthesis and Structures of Tetranuclear Cluster Complexes of Molybdenum [Mo_4 (mu_3-S) _2 (mu_2-S) _4X_2 (PMe_3) _6] (X=SH,Cl, Br, I,SCN) and [Mo_4 (mu_3-S) _2 (mu_2-S) _4 (dtc) _2 (PMe_3) _4]" J.Cluster Sci.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tsuge, H.Imoto, and T.Saito: "Syntheses, Structures, and Molecular-Orbital Calculations of Chromium Chevrel-Type Cluster Complexes [Cr_6E_8 (PR_3) _6] (E=S,PR_3=PEt_3, PMe_3 ; E=Se, Pr_3=REt_3, PMe_3, PMe_2Ph)" Bull.Chem.Soc.Jpn.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Taro Saito: Chalcogenide Cluster Complexes of the Early Transition Metals in "Early Transition Metal Clusters with pi-Donor Ligands", M.H.Chisholm ed.VCH,New York, 101 (1995)

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

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Published: 1997-03-04  

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