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Chemically Rational Modification of Integrated Cubane-type Frameworks

Research Project

Project/Area Number 02804051
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 InstitutionOkazaki National Research Institutes

Principal Investigator

ISOBE Kiyoshi  Okazaki National Research Institutes, Institute for Molecular Science, Associate Professor, 分子科学研究所, 助教授 (70101285)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1991: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1990: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsIntegrated Cubane-type Cluster / Triple Cubane-type / Trishomocubane-type / Quadruple Cubane-type / Partial Oxidation of Methanol / 積層立方体型クラスタ- / 四重キュバン型 / メタノ-ルの部分酸化 / 積層立方体型酸化物クラスタ- / 両親媒性 / 有機金属基の置換
Research Abstract

The exploitation of the reaction of the triple cubane-type cluster 1 with MeOH was undertaken to understand the heterogeneous MeOH/MoO_3 catalytic system. We found novel conversion, outlined in Scheme, of cluster 1 to trishomocubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](2) then to a linear quadruple cubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](3).
The molecular structure of clusters 2 and 3 were established by single crystal X-ray analyses and characterized by IR and NMR (^1H, and ^<13>C) spectroscopy. In cluster 2 the overall conformation of methoxy and Mo=O groups gives possible model for proton and non-redox methyl transfers involved in the MeOH/MoO_3 system, and cluster 3 is a congruent representation of the layer structure of MoO_3 recovered in the catalytic cycle of partial oxidation of MeOH. The clusters described here provide a novel synthetic example of extending topological equivalent of a recognizable unit in the infinite lattice.

Report

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

    (18 results)

All Other

All Publications (18 results)

  • [Publications] 小澤 芳樹,林 宜仁,磯邊 清: "Structure of Triammonium Hexahydrogen hexamolybdro-rhodata(III)Hexahydrate" Acta Cryst.C47. 637-638 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 林 宜仁,小澤 芳樹,磯邉 清: "Site Selective Oxygen-Exchange and Substitution of Organomelallic Group in Amphiphilic Quadruple-Cubane Type Cluster.Synthesis and Molecular Structure of 〔(MCp^*)_4V_6O_<19>〕(M=Rh_1Ir)" Inorg.Chem. 30. 1025-1033 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Young Kyu Do,Xiano-Zeng You Cuiji Zhang 小澤 芳樹 磯邉 清: "Trishomocubane-Type Methoxide Cluster as a Novel Mediator in the Extension of Cube Size in Organometallic Oxide Cluster:Synthesis and Structure of〔(RhCp^*)_2Mo_3O_9(OMe)_4〕、MeOH and a linear Auadruple Cubane-Type Cluster〔(RhCp^*)_4Mo_6O_<22>〕・4CH_2Cl_2(Cp^*=7^5=C_5Me_5)" J.Am.Chem.Soc. 113. 5892-5893 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 馬越 啓介,村田 勝夫,山下 伸典,磯邉 清: "Reactivity of〔Cp^*RhPtCl_6〕(Cp^*=7^5-C_5Me_5).Synthesis and Structures of〔(Cp^*Rh)_2(μ-Cl)_3〕〔PtCl_5(CH_3CONH_2)〕and〔(Cp^*Rh)_2(μ-Cl)_3〕_2〔PtCl_6〕" Inorg.Chim Acta. 190. 185-191 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 赤司 治夫,磯邉 清,小澤 芳樹,矢ヶ崎 篤: "β-Methallylrhodium(III)Supported on a Vanadium Oxide Cluster:Synthesis,Structure,and Reaction" J.Cluster Sci,. 2. 291-296 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Ozawa, Y. Hayashi, and K. Isobe: "Structure of Triammonium Hexahydrogenhexamolybdorhodate(III), Hexahydrate" Acta Cryst. C47. 637 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Hayashi, Y. Ozawa, and K. Isobe: "Site Selective Oxygen-Exchange and Substitution of Organometallic Groups in Amphiphilic Quadruple-Cubane Type Cluster. Synthesis and Molecular Structure of [(MCp*)_4V_6O_<19>](M=Rh,Ir)" Inorg. Chem. 30. 1025 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Do, X.-Z. You, C. Zhang, Y. Ozawa, and K. Isobe: "Trishomocubane-Type Methoxide Cluster as a Novel Mediator inthe Extension of of Cube Size in Organometallic Oxide Clusters: Synthesis and Structures of [(RhCp*)_2Mo_3O_9(OMe)_4] MeOH and a Linear Quadruple Cubane-Type Cluster [(RhCp*)_4Mo_6O_<22>]・4CH_2Cl_2(Cp*=eta^5-C_5Me_5)," J. Am. Chem. Soc. 113. 5892 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Umakoshi, K. Murata, S. Yamashita, and K. Isobe: "Reactivity of [Cp*RhPtCl_6 (Cp*=eta^5-C_5Me_5). Synthesis and Structures of [Cp*Rh)_2(mu-Cl)_3[PtCl_5(CH_3CONH_2)] and [(Cp*Rh)_2(mu-Cl)_3]_2[PtCl_6]" Inorg. Chim. Acta. 190. 185 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] H. Akashi, K. Isobe, Y. Ozawa, and A. Yagasaki: "beta-Methallylrhodium(III) Supported on a Vanadium Oxide Cluster: Synthesis, Structure, and Reaction" J. Cluster Sci. 2. 291 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 小澤 芳樹,林 宜仁,磯邉 清: "Structure of Triammonium Hexahydrogen hexamolybdrorhodata(III)Hexahydrate" Acta Cryst.C47. 637-638 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 林 宜仁,小澤 芳樹,磯邉 清: "Site Selective OxygenーExchange and Substitution of Organomelallic Group in Amphilic AuadrupleーCubabane Type Cluster.Synthesis and Molecular Structure of 〔(MCp)_4V_6O_<19>〕(M=Rh,Ir)" Inorg,Chem,. 30. 1025-1033 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Youngkyu Do;XiaoーZeng You;Cuiji Zhang:小澤 芳樹,磯邉 清: "Trishomocubane-Type Methoxide Cluster asa Novel Mediator in the Extension of Cube Size in Organometallic Oxide Cluster :Synthesis and Strueture of 〔(RhCp^*)_2Mo_3O_9(OMe)_4〕・MeOH and a linear Auadruple Cubane-Type Cluster 〔(RhCp^*)_4Mo_6O_<22>〕・4CH_2Cl_2(Cp^*=C_5Me_5)" J.Am.Chem.Soc.113. 5892-5893 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 馬越 啓介,村田 勝夫,山下 伸典,磯邉 清: "Reqctirity of 〔C^*RhP+cl_6〕(CP^*=7^5ーC_5Me_5)ーSynthesis and Structures of 〔(Cp^*Rh)_2(μーcl)_3〕〔Ptcl_5(CH_3CONH_2)〕and 〔(Cp^*Rh)_2(μーcl)_3〕_2〔Ptcl_6〕" Inorg.Chim Acta. 190. 185-191 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 赤司 治夫,磯邉 清,小邉 芳樹,矢ケ崎 篤: "βーMethallylrhodium(III)Supported on a Vanadium Oxide Cluster:Synthesis,Structure,and Reaction" J.Cluster Sci. 2. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 小澤 芳樹,林 宜仁,磯邉 清: "Structure of Triammonium Hexahydrogenhexamolybdorhoclate(III),Hevahydrate" Acta Cryst.,Aection C. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] 林 宜仁,小澤 芳樹,磯邉 清: "Site Selective OxygenーExchange and Substitution of organometallic Group in Amphiphilic QuadrupleーCubane Type Cluster.Synthesis and Molecular Structure of[(MCp^*)_4V_6O_<19>](M=Rh,Ir)" Inorg.Chem.,. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Youngkyudo,XiaoーZengyou,Cuiji Zhang,小澤 芳樹,磯邉 清: "TrishomocubaneーTypeMethoxide Cluster asa Novel Mediator in the Extension of Cube Size in Organometallic Oxide Cluster:Synthesis and Structure of[(RhCP^*)_2Mo_3O_9(OMe)_4]・MeOH and a Linear Quadruple CubaneーType Cluster [(RhCp^*)_4Mo_6O_<22>]・4CH_2Cl_2(Cp^*=7^5ーC_5Me_5)" J.AM.Chem.Soc.,.

    • Related Report
      1990 Annual Research Report

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

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