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2006 Fiscal Year Final Research Report Summary

Syntheses of Chalcogenklo-Bridged Transition Metal Clusters

Research Project

Project/Area Number 14078206
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionThe University of Tokyo

Principal Investigator

MIZOBE Yasushi  The University of Tokyo, Institute of Industrial Science, Professor, 生産技術研究所, 教授 (40175609)

Project Period (FY) 2002 – 2005
KeywordsMetal cluster / Sulfido cluster / Selenido cluster / Thiolato complex / Metalloenzyme model / Mixed-metal polynuclear complex / Nitrogen fixation / Supramolecule synthesis
Research Abstract

1. Novel hydrosulfido-and hydroselenido-bridged dinudear complexes of Ir, Rh, and Ru containing the M(μ-EB)_2M cores (E=S, Se) have been isolated, which have proved to serve as versatile precursors to synthesize a variety of chalcogenido bridged homo-and hetermetallic clusters through dimerizartion or by treatment with certain transition metal compounds as well as main group metal species. The nuclearities of the produced dusters vary from three to seven. Trinuclear sulfido-thiolato duster of Ir [(Cp^*Ir)_3(_<μ3>-S)(_<μ2>-SH)_3]Cl has also been prepared, which has been found to be converted to a series of cubane-type Ir_3MS_4 dusters by incorporating certain M fragments.
2. Sulfido-bridged dinudear complexes of Mo, W, and Re containing the MS(μ-S)_2MS cores have been converted to a variety of incomplete cubane-type and cubane-type mixed-metal sulfido dusters. It is to be noted that trimetallic cubanes are readily available from Re precursor by the stepwise addition of two different metal sources.
3. Mixed-metal cubane-type Mo_2M_2S_4 dusters with oxo ligand (M=Ir, Rh) have been prepared, which have been found to catalyze the N-N bond cleaving reaction of methylphenylhydrazine in the presence of a proton source and reducing agent. Hydrazido duster as an intermediate stage of this nitrogenase model reaction has also been isolated and fully characterized.
4. Sulfido-and thiolato-bridged In and Ir2Ru dusters have been prepared and their reactivities toward small molecules such as CO, isocyanide, and alkynes investigated. For the former Ir3 duster, its ability to catalyze highly stereoselective cydotrimerization of terminal alkyne has been demonstrated.

  • Research Products

    (39 results)

All 2006 2005 2004 2003

All Journal Article (38 results) Book (1 results)

  • [Journal Article] DFT Calculations of the Cubane-Type Mo_2Ru_2S_4 Clusters2006

    • Author(s)
      Kazunari Yoshizawa
    • Journal Title

      Bull. Chem. Soc. Jpn. 79

      Pages: 53-58

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Addition of Benzenethiol to Terminal Alkynes Catalyzed by Hydrotris(3,5-dimethylpyrazol)borate-Rh(III) Bis(thiolate)2006

    • Author(s)
      Yoshiyuki Misumi
    • Journal Title

      J. Organomet. Chem. 691

      Pages: 3157-3164

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] DFT Calculations of the Cubane-Type Mo2Ru2S4 Clusters. Stability of the Possible Dinitrogen Cluster and the Isolable Acetonitrile Cluster2006

    • Author(s)
      K.Yoshizawa, N.Kihara, Y.Shiota, H.Seino, Y.Mizobe
    • Journal Title

      Bull. Chem. Soc. Jpn. 79

      Pages: 53-58

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Addition of Benzenethiol to Terminal Alkynes Catalyzed by Hydrotris(3,5-dimethylpyrazolyl)borate-Rh(III) Bis(thiolate) Complex : Mechanistic Studies with Characterization of the Key Intermediates2006

    • Author(s)
      Y.Misumi, H.Seino, Y.Mizobe
    • Journal Title

      J. Organomet. Chem. 691

      Pages: 3157-3164

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Mixed-Metal Sulfido Clusters Containing Noble Metals and Group 15 Metals. Stepwise Construction of Bimetallic and Trimetallic Ru2MS2 (M = Sb, Bi), Ru2PdSbS2, and Ru2Pd2SbS2 Cores2006

    • Author(s)
      T.Amitsuka, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Organometallics 25

      Pages: 3034-3039

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reaactions of Hydrosulfido- and Hydroselenido-Bridged Dinuclear Ir, Rh, and Ru Complexes with SbCl_3 and BiCl_32005

    • Author(s)
      Wenn-Yan Yeh
    • Journal Title

      J. Organomet. Chem. 689

      Pages: 2338-2345

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation and Structures of the Cluster Consisting of Rh_2Mo_2S_4 Single-Cubane Units Connected by Two Bidentate N-Donor Ligands2005

    • Author(s)
      Tomoko Fujimura
    • Journal Title

      Inorg. Chim. Acta 358

      Pages: 2449-2453

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Chalcogenido-Bridged Dinuclear Tp*Rh-Cp*Ru Complexes and Binding of Dioxygen to Their Ru Sites2005

    • Author(s)
      Shoken Nagao
    • Journal Title

      Dalton Trans.

      Pages: 3166-3172

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Research Inspired by the Chemistry of Nitrogenase - Novel Metal Complexes and Their Reactivity2005

    • Author(s)
      Masanobu Hidai
    • Journal Title

      Can. J. Chem. 83

      Pages: 358-374

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Rhodium Pentasulfido(2-) Complexes with Hydrotris-(3,5-dimethylpyrazol-1-yl)borato Coligand2005

    • Author(s)
      Shoken Nagao
    • Journal Title

      Bull. Chem. Soc. Jpn. 78

      Pages: 1641-1643

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of a Sulfido- and Thiolato-Bridged Trinuclear Bimetallic Clusters and Its Reactions2005

    • Author(s)
      Hidenobu Kajitani
    • Journal Title

      Organometallics 24

      Pages: 6260-6267

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Mixed-Metal Sulfido Clusters Containing Noble Metals and Group 15 Metals2005

    • Author(s)
      Takahiko Amitsuka
    • Journal Title

      Organometallics

      Pages: 3166-3172

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation and Structures of the Cluster Consisting of Rh2Mo2S4 Single- Cubane Units Connected by Two Bidentate N-Donor Ligands2005

    • Author(s)
      T.Fujimura, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Inorg. Chim. Acta 358

      Pages: 2449-2453

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Rhodium Pentasulfido(2-) Complexes with Hydrotris(3,5-dimethylpyrazol-1-yl)borato Coligand2005

    • Author(s)
      S.Nagao, N.Saito, A.Kojima, H.Seino, Y.Mizobe
    • Journal Title

      Bull. Chem. Soc. Jpn. 78

      Pages: 1641-1643

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Chalcogenolato-Bridged Dinuclear Tp*Rh-Cp*Ru Complexes and Their Binding of Dioxygen to Their Ru Sites2005

    • Author(s)
      S.Nagao, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Dalton Trans.

      Pages: 3166-3172

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of a Sulfido-and Thiolato-Bridged Trinuclear Bimetallic Cluster [{(C5Me5)1r}2{(C5Hs)Ru}Cl(p3-S)(p2-SCH2CH2CN)2] and Its Reactions with CO, lsocyanide, and Alkyne2005

    • Author(s)
      H.Kajitani, H.Seino, Y.Mizobe
    • Journal Title

      Organometallics 24

      Pages: 6260-6267

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Research Inspired by the Chemistry of Nitrogenase-Novel Metal Complexes and Their Reactivity towards Dinitrogen, Nitriles, and Alkynes2005

    • Author(s)
      M.Hidai, Y.Mizobe
    • Journal Title

      Can. J. Chem. 83

      Pages: 358-374

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] One- or Two-Dimensional Organometallic Arrays Containing PdIr_2(μ_3-S)_2 Mixed-Metal Sulfido Cluster Units2004

    • Author(s)
      Tomoko Fujimura
    • Journal Title

      J. Organomet. Chem. 689

      Pages: 738-743

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Mononuclear and Dinuclear Rh Hydrotris(pyrazolyl)-borato Complexes Containing Arenethiolato Ligands2004

    • Author(s)
      Hidetake Seino
    • Journal Title

      Dalton Trans.

      Pages: 3593-3600

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and X^Ray Structure of the New Mo Diselenido Complex with Hydrotris(pyrazolyl)gorate Coligand [Et_4N][TpMo(CO)_2(Se_2)]2004

    • Author(s)
      Shoken Nagao
    • Journal Title

      Inorg. Chim. Acta 357

      Pages: 4618-4621

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] One-or Two-Dimensional Organometallic Arrays Containing Pdlr2(p3-S)2 Mixed-Metal Sulfido Cluster Units Connected via the Nicotinamide or Isonicotinamide Ligands on Their Pd Sites through Hydrogen-Bonding Interactions2004

    • Author(s)
      T.Fujimura, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      J. Organomet. Chem. 689

      Pages: 738-743

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reactions of Hydrosulfido-and Hydroselenido-Bridged Dinuclear Ir, Rh, and Ru Complexes with SbCI3 and BiCI3 Affording Mixed-Metal Sulfido and Selenido Clusters Containing Both Noble Metals and Group 15 Metal2004

    • Author(s)
      W.-Y.Yeh, H.Seino, T.Amitsuka, S.Ohba, M.Hidai, Y.Mizobe
    • Journal Title

      I. Organomet. Chem. 689

      Pages: 2338-234

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Mononuclear and Dinuclear Rh Hydrotris(pyrazolyl)borato Complexes Containing Arenethiolato Ligands and Conversion of the Mononuclear Complex into Dinuclear Rh-Rh and Rh-Ir Complexes with Bridging Arenethiolato Ligands2004

    • Author(s)
      H.Seino, T.Yoshikawa, M.Hidai, Y.Mizobe
    • Journal Title

      Dalton Trans.

      Pages: 3593-3600

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis and X-Ray Structure of the New Mo Diselenido Complex with Hydrotris(pyrazolyl)borate Coligand [EtaN][TpMo(C0)2(Se2)]2004

    • Author(s)
      S.Nagao, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Inorg. Chim. Acta 357

      Pages: 4618-4621

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of Heterobimetallic Cluster with Bridging Sulfido and Thiolato Ligands [{(C_5Me_5)Ru}{C_5Me_5)Ir_2}(μ_3-S)(μ_2-SCH_2CH_CN)_2Cl]2003

    • Author(s)
      Fusao Takagi
    • Journal Title

      Organometallics 22

      Pages: 1065-1071

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of a Series of Trinuclear MIr_II or Pentanuclear MIr_4 Bimetallic Bis(selenido) and Selenido-Sulfido Clusters2003

    • Author(s)
      Shoken Nagao
    • Journal Title

      J. Organomet. Chem. 669

      Pages: 124-134

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cubane-Type Heterobimetallic Sulfido Clusters : Incorporation of Two Metal Fragments into a Dinuclear ReS(μ-S)_2ReS Core2003

    • Author(s)
      Hidetake Seino
    • Journal Title

      Inorg. Chem. 42

      Pages: 4585-4596

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Bimetallic Cubane-Type Mo_IIM_IIS_4 Clusters and Reductive Cleavage of N-N bond in 1,1-Methylphenylhydrazine2003

    • Author(s)
      Hidetake Seino
    • Journal Title

      Organometallics 22

      Pages: 3424-3431

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] A Series of Dinuclear Homo- and Heterometallic Complexes with Two or Three Bridging Sulfido Ligands2003

    • Author(s)
      Hidetake Seino
    • Journal Title

      Inorg. Chem. 42

      Pages: 7387-7395

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Transformations of the Incomplete Cubane-Type Ir_3S(SH)_III Cluster into Heterometallic Clusters2003

    • Author(s)
      Aya Shinozaki
    • Journal Title

      Organometallics 22

      Pages: 4636-4638

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Cubane-Type Mo_3NiS_4 Clusters and Their Catalytic Activity for the Cyclization of Alkyoic Acids to Enol Lactons2003

    • Author(s)
      Izuru Takei
    • Journal Title

      Organometallics 22

      Pages: 4636-4638

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of Heterobimetallic Cluster with Bridging Sulfido and Thiolato Ligands [{C5Me5}Ru]{(C5Me5)10.2(p3-S)(p2-SCH2CH2CN)2C1] and Its Transformation into Alkyne, CO, Isocyanide, and Iminoacyl Clusters2003

    • Author(s)
      F.Takagi, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Organometallics 22

      Pages: 1065-1071

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Syntheses of a Series of Trinuclear MIr2 or Pentanuclear MIN Bimetallic Bis(selenido) and Selenido-Sulfido Clusters (M = Pd, Pt, Fe, Co) from Diiridium p-Bis(hydroselenido) and p-Hydroselenido-Hydrosulfido Complexes2003

    • Author(s)
      S.Nagao, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      J. Organomet. Chem. 669

      Pages: 124-134

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cubane-Type Heterometallic Sulfido Clusters : Incorporation of Two Metal Fragments into a Dinuclear ReS(p-S)2ReS Core Affording Bimetallic Cluster or Trimetallic Clusters via Incomplete Cubane-Type MRe2(p3-S)(p2-S)3 Intermediates2003

    • Author(s)
      H.Seino, T.Kaneko, S.Fujii, M.Hidai, Y.Mizobe
    • Journal Title

      Inorg. Chem. 42

      Pages: 4585-4596

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Bimetallic Cubane-Type Mo2M2S4 Clusters and Reductive Cleavage of N-N Bond in 1,1-Methylphenylhydrazine Affording N-Methylaniline Using Mo2Ir2S4 and Mo2Rh2S4 Clusters as Catalyst Precursor2003

    • Author(s)
      H.Seino, T.Masumori, M.Hidai, Y.Mizobe
    • Journal Title

      Organometallics 22

      Pages: 3424-3431

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A Series of Dinuclear Homo-and Heterometallic Complexes with Two or Three Bridging Sulfido Ligands Derived from the Tungsten Tris(sulfido) Complex [Et4N][(Me2Tp)WS3]2003

    • Author(s)
      H.Seino, N.Iwata, N.Kawarai, M.Hidai, Y.Mizobe
    • Journal Title

      Inorg. Chem. 42

      Pages: 7387-7395

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Transformations of the Incomplete Cubane-Type Ir3S(SH)3 Cluster into the Single Cubane-Type, Corner-Shared Double Cubane-Type, and Cuboida Heterometallic Clusters2003

    • Author(s)
      A.Shinozaki, H.Seino, M.Hidai, Y.Mizobe
    • Journal Title

      Organometallics 22

      Pages: 4636-4638

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Cubane-Type Mo3NiS4 Clusters and Their Catalytic Activity for the Cyclization of Alkynoic Acids to Enol Lactones2003

    • Author(s)
      I.Takei, Y.Wakebe, K.Suzuki, Y.Enta, T.Suzuki, Y.Mizobe, M.Hidai
    • Journal Title

      Organometallics 22

      Pages: 4639-4641

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] Handbook of Chalcogen Chemistry2006

    • Author(s)
      Yasushi Mizobe
    • Total Pages
      16
    • Publisher
      Royal Society of Chemistry
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2008-05-27  

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