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Synthesis of Manganese Oxide Clusters with Oxidation Catalysis

Research Project

Project/Area Number 11640569
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

ISOBE Kiyoshi  Faculty of Science, Osaka City University Professor, 理学部, 教授 (70101285)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordsoxidation catalysis / oxometalate / tacn complex / Cp^*Rh-W oxide cluster / ESI-mass spectrometer / windmill type / triple cubane type / sprayer for measurement of short live species / 立方体型(tacn)Mn-Mo系クラスター / 金属酸化物複合体
Research Abstract

We synthesized Mn-Mo and Rh-W oxide clusters with tacn (1,4,7-triazacyclononane) derivatives and Cp (cyclopentadienyl) ligands, respectively. Their ability of oxidation catalysis for hydrocarbon compounds was examined.
A reaction of the dinuclear oxometalate of [(n-Bu_4)N]_2[Mo_2O_7] and (tacn) MnCl_3 in water afforded a new cubic type of the Mn-Mo mixed metal oxide cluster of [{(tacn)Mn}_2Mo_4O_<16>]-4H_2O (1). An X-ray analysis of 1 reveals that it is composed of a cubic framework consisting of one Mn(IV), three Mo (VI) ions and four oxygen atoms. It also has an incomplete cubic framework formed by three Mo (VI) ions and four oxygen atoms.
We examined catalytic ability of 1 towards the bleaching of pinacyanol chloride dye (PC dye). In the reaction using 1 the blue color of the dye disappeared in 6h in water under heterogeneous conditions : hydrogen peroxide (15 mol), PC dye (15 mol) and catalyst (1.5 mol). This preliminaly results show that cluster 1 is able to use a mild bleaching catalyst for a heterogeneous system.
Rh-W oxide clusters with the Cp^* ligand were prepared in two geometrical isomers of [(Cp^*Rh)_4W_4O_<16>] from the reaction of the mononuclear [WO_4]^<2-> with [Cp^*RhCl(μ-Cl)]_2 in CH_3CN : two geometrical isomers have a windmill and a triple cubane geometrical framework. The former was formed selectively below 20℃. Above 60℃ the latter was obtained specifically in the same reaction system. We studied the mechanisms for the isomerization and the formation of those isomers by using ^<17>O NMR spectroscopy and ESI-MS.It is found that a species with a ladder structure plays an important role for both the isomerization and the formation of the isomers.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Kentaro Kimura,Takahiro Kimura,Isamu Kinoshita,Nobuaki Nakashima,Kenich Kitano,Takanori Nishioka,Kiyoshi Isobe: "Aerobic Oxidation of a Disulfide to its Sulfonate Leading to Supramolecular Pyridine-2-sulfonato Cu(II) and Zn(II) Complexes"Chem.Commun.. 497-498 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Rimo Xi,Bateer Wang,Masaaki Abe,Yoshiki Ozawa,Isamu Kinoshita.and Kiyoshi Isobe,: "Tetranuclear Mo2Rh2 Complexes Obtained from Reactions between Triple Cubane-type Oxide Cluster [(Cp^*Rh)4Mo4O16](Cp^*=η5-C5(CH3)5) and Methanethiol;"Bull.Chem.Soc.Jpn.. 72. 1985-1996 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Satoshi Takara,Seiji Ogo,Yoshihito Watanabe,Koji Nishikawa,Isamu Kinoshita and Kiyoshi Isobe: "Direct Observation by Electrospray Ionization Mass Spectrometry of a Key Intermediate [Cp^*RhMo3O8(OMe)5]-(Cp^*=η5-C5Me5) in the Formation of a Double-Bookshelf-type……"Angew.Chem.Int.Ed.. 38. 3051-3053 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hideaki Takagi,Akio Ichimura,Toshihiro Yano,Isamu Kinoshita,Kiyoshi Isobe 他9名: "Feasible Attachment of a Dinuclear Ruthenium Complex to Gold Electrode Surfaces. A Screening Method to Find Functional Electrodes"Electrochemistry. 67. 1192-1193 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koji Nishikawa,Isamu Kinoshita,Takanori Nishioka,and Kiyoshi Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 1342-1343 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kenichi Kitano,Rika Tanaka,Takahiro Kimura,Toshiyuki Tsuda,Seiji Shimizu,Hideaki Takagi,Takanori Nishioka,Daisuke Shimoi,Akio Ichimura,Isamu Kinoshita,Kiyoshi Isobe,and Shun ichiro Ooi: "Lantern-type Dinuclear CrIIIPtII and VIVPtII Complexes Bridged by Pyridine-2-thiolate. Synthesis and Characterization."J.Chem.Soc.Dalton Trans.. 995-1000 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiroshi Shimomura,Takanori Nishioka,Masaaki Abe,Isamu Kinoshita and Kiyoshi Isobe: "Formation of μ4-Se2 Complex by the Oxidative Coupling of μ-SeH Complex : Double-site Atomic Inversion of the μ4-Se2 Complex [{(Cp^*Rh)2(μ-CH2)2}2(μ4-Se2)]^<2+>(Cp^*=η5-C_5Me_5)"J.Organomet.Chem.. 611. 386-391 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kentaro Kimura, Takahiro Kimura, Isamu Kinoshita, Nobuaki Nakashima, Ken'ichi Kitano, Takanori Nishioka, Kiyoshi Isobe: "Aerobic Oxidation of a Disulfide to its Sulfonate Leading to Supramolecular Pyridine-2-sulfonato Cu(II) and Zn(II) Complexes"Chem.Commun.. 497-498 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Rimo Xi, Bateer Wang, Masaaki Abe, Yoshiki Ozawa, Isamu Kinoshita, and Kiyoshi Isobe: "Tetranuclear Mo2Rh2 Complexes Obtained from Reactions between Triple Cubane-type Oxide Cluster [(Cp^*Rh)4Mo4O16] (Cp^*=η5-C5(CH3)5) and Methanethiol"Bull.Chem.Soc.Jpn.. 72. 1985-1996 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Satoshi Takara, Seiji Ogo, Yoshihito Watanabe, Koji Nishikawa, Isamu Kinoshita, and Kiyoshi Isobe: "Direct Observation by Electrospray Ionization Mass Spectrometry of a Key Intermediate [Cp^*RhMo3O8(OMe)5] (Cp^*=η5-C5Me5) in the Formation of a Double-Bookshelf-typ Oxide Cluster [(Cp^*Rh)2Mo6O20(OMe)2]^2"Angew.Chem.Int.Ed.. 38. 3051-3053 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hideaki Takagi, Akio Ichimura, Toshihiro Yano, Isamu Kinoshita, Kiyoshi Isobe, and other 9 people: "Feasible Attachment of a Dinuclear Ruthenium Complex to Gold Electrode Surfaces. A Screening Method to Find Functional Electrodes"Electrochemistry. 67. 1192-1193 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koji Nishikawa, Isamu Kinoshita, Takanori Nishioka, and Kiyoshi Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 1342-1343 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ken'ichi Kitano, Rika Tanaka, Takahiro Kimura, Toshiyuki Tsuda, Seiji Shimizu, Hideaki Takagi, Takanori Nishioka, Daisuke Shimoi, Akio Ichimura, Isamu Kinoshita, Kiyoshi Isobe, and Shun'ichiro Ooi: "Lantern-type Dinuclear CrIIIPtII and VIVPtII Complexes Bridged by Pyridine-2-thiolate. Synthesis and Characterization."J.Chem.Soc.Dalton Trans.. 995-1000 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiroshi Shimomura, Takanori Nishioka, Masaaki Abe, Isamu Kinoshita and Kiyoshi Isobe: "Formation of μ4-Se2 Complex by the Oxidative Coupling of μ-SeH Complex : Double-site Atomic Inversion of the μ4-Se2 Complex [{(Cp^*Rh)2(μ-CH2)2}2(μ4-Se2)]_<2+> (Cp^*=η5-C5Me5)"J.Organomet.Chem.. 611. 386-391 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Koji Nishikawa,Isamu Kinoshita,Takanori Nishioka,and Kiyoshi Isobe: "Synthesis and X-Ray Analysis of Mn-Mo Mixed Metal Oxide Cluster with Cubic Framework"Chem.Lett.. 1342-1343 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Ken'ichi Kitano,Rika Tanaka,Takahiro Kimura,Toshiyuki Tsuda.Seiji Shimizu,Hideaki Takagi,Takanori Nishioka,Daisuke Shimoi,Akio Ichimura,Isamu Kinoshita,Kiyoshi Isobe,and Shun'ichiro Ooi : "Lantern-type Dinuclear CrIIIPtII and VIVPtII Complexes Bridged by Pyridine-2-thiolate. Synthesis and Characterization."J.Chem.Soc.Dalton Trans.. 995-1000 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Hiroshi Shimomura,Takanori Nishioka,Masaaki Abe,Isamu Kinoshita and Kiyoshi Isobe: "Formation of μ4-Se2 Complex by the Oxidative Coupling of μ-SeH Complex : Double-site Atomic Inversion of the μ4-Se2 Complex [{(Cp^*Rh)2(μ-CH2)2}(μ4-Se2)]2+(Cp^*=η5-C5Me5)"J.Organomet.Chem.. 611. 386-391 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kentaro Kimura, Takahiro Kimura, Isamu Kinoshita, Nobuaki Nakashima, Ken'ichi Kitano, Takanori Nishioka, Kiyoshi Isobe: "Aerobic oxidation of a disulfide to its sulfonate leading to supramolecular pyridine-2-sulfonato Cu(II) and Zn(II) complexes"Chem. Commun.. 497-498 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Rimo Xi, Bateer Wang, Masaki Abe, Yoshiki Ozawa, Isamu Kinoshita, and Kiyoshi Isobe,: "Tetranuclear Mo2Rh2 Complexes Obtained from Reactions between Triple Cubane-type Oxide Cluster [(Cp^*Rh)4Mo4O16](Cp^*=h5-C5(CH3)5) and Methanethiol"Bull. Chem. Soc. Jpn.. 72. 1985-1996 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Satoshi Takara, Seiji Ogo, Yoshihito Watanabe, Koji Nishikawa, Isamu Kinoshita, and Kiyoshi Isobe: "Direct Observation by Electrospray Ionization Mass Spectrometry of a Key Intermediate [Cp^*RhMo3O8(OMe)5]-(Cp^*=h5-C5Me5) in the Formation of a Double-Bookshelf-type・・・・・・・・・・・・"Angew. Chem. Int. Ed.,. 38, No.20. 3051-3053 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hideki Takagi, Akio Ichimura, Toshihiro Yano, Isamu Kinoshita, Kiyoshi Isobe 他9名: "Feasible Attachment of a Dinuclear Ruthenium Complex to Gold Electrode Surfaces. A Screening Method to Find Functional Electrodes"Electrochemistry. 67. 1192-1193 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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