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2006 Fiscal Year Final Research Report Summary

Control of Electronic Envionment ofReadion Site ofTransition Metal Cluster Complexes

Research Project

Project/Area Number 14078210
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTokyo Institute of Technology

Principal Investigator

SUZUKI Hiroharu  Tokyo Institute of Technology, Graduate School of Science and Engineering, Professor, 大学院理工学研究科, 教授 (30106629)

Project Period (FY) 2002 – 2005
Keywordsnolyhydrido cluster / ruthenium / hydrazine / activation of ammonia / heterometallic cluster / N-N bond cleavage
Research Abstract

1. Synthesis of Tetra-and Pentanuclear Ruthenium Polyhydrido Clusters : The reactivity of cluster complex is most probably affected by the nuclearity because the reactivity strongly depends on the number of transferable electrons between the cluster and substrate. Thus the development of a rational method for the synthesis of clusters with higher nuclearity and a variety of auxiliary ligands seems to be essential for the application of such cluster to organic synthesis. After a four-year term of the research, we developed synthetic methods of a variety of tetra-and pentanuclear ruthenium polyhydrido clusters, such as (CpRu)_4H_6, (CpRu)_3(Cp^*Ru)H_6, (CpRu)_2(Cp^*Ru)_2H_6, (CpRu)(Cp^*Ru)_3H_6, and (CpRu)_5H_7. Electronic properties of these clusters were estimated by means of electrochemical technique.
2. Synthesis of Di-and Trinuclear Heterobimatallic Polyhydrido Clusters Containing Molybdenum, Tungsten, Rhenium, and Ruthenium : Novel heterotrimetallic polyhydrido complexes containing … More ruthenium and group 6 metals,
(Cp^*Ru)_2(Cp^*M)(μ-H)_5 (M = Mo, W) and (Cp^*Ru)(Cp^*W)_2H_7, were synthesize by the reaction of (Cp^*RuOMe)_2 with dinuclear polyhydrido complexes Cp^*Ru(μ-H)_3MH_3Cp^* (M = Mo, W). Polyhydrido complexes containing both ruthenium and rhenium, Cp^*Ru(μ-H)_3ReH_2Cp^* and (Cp^*Ru)_2(Cp^*Re)(μ-H)_7, were also synthesized.
3. Cleavage of the N-N Bond of Hydrazine Induced by Triruthenium Cluster : The reaction of [(Cp^*Ru)_3H_6]+ with hydrazine led to the the formation of (Cp^*Ru)_3(μ-NH)H_3 as a result of cleavage of the N-N bond. This compound further reacted with hydrazine to yield (Cp*Ru)_3(μ-NH)_2H. These μ_3-imido complexes underwent hydrogenation to generate (Cp^*Ru)_3H_5 together with liberation of ammonia.
4. Cleavage of N-H Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters : Ruthenium polyhydrido cluster (Cp^*Ru)_3H_5 reacted with ammonia to produce a mono-μ_3imido complex and dihydrogen as a result of activation of the two N-H bonds. The N-H bond cleavage was accelerated in the reaction with a proxo complex, (Cp^*Ru)_3(μ-O)(μ-H)_3. Less

  • Research Products

    (44 results)

All 2006 2005 2004 2003 2002

All Journal Article (44 results)

  • [Journal Article] Cleavage of the C-N Triple Bond on the Triruthenium Cluster. Synthesis and Structure of a Triruthenium Complex Containing a M3-Nitrido Ligand2006

    • Author(s)
      川島敬史, 高尾俊郎, 鈴木寛治
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 485-488

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cleavage of Nitrogen-Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters2006

    • Author(s)
      中島裕美子, 亀尾 肇, 鈴木寛治
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 950-952

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Group 8-Group 6 Heterotrimetallic Polyhydrido Complexes Having Only a C_5Me_5 Group as Auxiliary Ligand2006

    • Author(s)
      伊藤淳一, 島 隆則, 鈴木寛治
    • Journal Title

      Organometallics 25

      Pages: 1333-1336

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cleavage of the C-N Triple Bond on the Triruthenium Cluster : Synthesis and Structure of a Triruthenium Complex Containing a m3-Nitrido Ligand2006

    • Author(s)
      T.Kawashima, T.Takao, H.Suzuki
    • Journal Title

      Angew. Chem. Mt. Ed. 45

      Pages: 485-488

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cleavage of a Nitrogen-Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters2006

    • Author(s)
      Y.Nakajima, H.Kameo, H.Suzuki
    • Journal Title

      Angew. Chem. Mt. Ed. 45

      Pages: 950-952

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Group 8-Group 6 Heterotrimetallic Polyhydrido Complexes Having Only a C5Me5 Group as Auxiliary Ligand2006

    • Author(s)
      J.Ito, T.Shima, H.Suzuki
    • Journal Title

      Organometallics 25

      Pages: 1333-1336

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] P-C Bond Cleavage by a Heterobimetallic Polyhydrido Complex, (C_5Me_5)Ru(μ*H)_3Ir(C_5Me_5). Structure Determination and Fluxional Behavior of a Bridging Phosphido Complex, (C_5Me_5)Ru(μ-PPh_)(μ-η1 : η^2-C_6H_5)Ir(C_5Me_5)2005

    • Author(s)
      島 隆則, 鈴木寛治
    • Journal Title

      Organometallics 24

      Pages: 1703-1708

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Nitrogen^Nitrogen Double Bond Cleavage of Azobenzene by a Triruthenium Pentahydrido Complex, (Cp'Ru)_3(μ_3H_2)_2(μ-H)_2(μ-H)_3(Cp'=η^5-C_5Me_), and Catalytic Hydrogenation of Azobenzene and1,2-Diphenyhydrazine2005

    • Author(s)
      中島裕美子, 鈴木寛治
    • Journal Title

      Organometallics 24

      Pages: 1860-1866

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Structure of a Triruthenium Complex Containing a Perpendicularly Coordinated μ_3-η^2 : η^2(⊥)-Nitrile Ligand, and Its Protonation to Yield a Perpendicularly Coordinated Iminoacyl Ligand2005

    • Author(s)
      高尾俊郎, 川島敬史, 松原公紀, 鈴木寛治
    • Journal Title

      Organometallics 24

      Pages: 3371-3374

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Heterobimetallic Polyhydride Complex, Cp^*Ru(μ-H9_4OsCp^*(Cp^*=η^5-C_5Me_5). Synthesis and Reaction with Ethylene2005

    • Author(s)
      島 隆則, 鈴木寛治
    • Journal Title

      Organometallics 24

      Pages: 3939-3945

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis, Structures, and Reactions of Coordinatively Unsaturated Trinuclear Ruthenium Polyhydrido Complexes, [{Ru(C5Me5)}3(-H)6]O') (Y = BF4, CF3SO3, 1n(so4), c6H5c02, a-13002, B(C6H5)4, PF6) and [{Ru(C5Me5)}3(441)3013-1-02]2005

    • Author(s)
      H.Suzuki, T.Kakigano, K.Tada, M.Igarashi, K.Matsubara, A.Inagaki, M.Oshima, T.Takao
    • Journal Title

      Bull. Chem. Soc. Jpn. 78

      Pages: 67-87

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] P-C Bond Cleavage by a Heterobimetallic Polyhydrido Complex, (C5Me5)Ru(ti-H)3Ir(C5Me5). Structure Determination and Fluxional Behavior of a Bridging Phosphido Complex, (c5Me5)Ru(y-PPh2)(y- : 772-C6H5)Ir(C5Me5)2005

    • Author(s)
      T.Shima, H.Suzuki
    • Journal Title

      Organometallics 24

      Pages: 1703-1708

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Nitrogen-Nitrogen Double Bond Cleavage of Azobenzene by a TrirutheniumuPentahydrido Complex, (Cp'Ru)3(4u3-H)2(p-H)3 (Cp' = //5-05Me5), and Catalytic Hydrogenation of Azobenzene and 1,2-Diphenylhydrazine2005

    • Author(s)
      Y.Nakajima, H.Suzuki
    • Journal Title

      Organometallics 24

      Pages: 1860-1866

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis and Structure of a Triruthenium Complex Containing a Perpendicularly Coordinated /43-772 : 7/2( )-Nitrile Ligand, and Its Protonation to Yield a Perpendicularly Coordinated Iminoacyl Ligand2005

    • Author(s)
      T.Takao, T.Kawashima, K.Matsubara, H.Suzuki
    • Journal Title

      Organometallics 24

      Pages: 3371-3374

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Heterobimetallic Polyhydride Complex, Cp*Ru(y-H)40sCp* (Cp* = if-05Me5). Synthesis and Raction with Ethylene2005

    • Author(s)
      T.Shima, H.Suzuki
    • Journal Title

      Organometallics 24

      Pages: 3939-3945

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Di-and Trinuclear Polyhedride Complexes Containing Ruthenium and Rhenium. Synthesis, Site Exchange, and H/D Exchange of Hydride Ligands2004

    • Author(s)
      伊藤淳一, 島 隆則, 鈴木寛治
    • Journal Title

      Organometallics 23

      Pages: 2447-2460

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Reductive Cleavage of the N-N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex,[(Cp'Ru)_3(μ-H_6]X(Cp'=η^5-C_5Me_5; X=1/2 SO_4m BF_4, PF_6, BPh_4) and Dihydrogen2004

    • Author(s)
      中島裕美子, 稲垣昭子, 鈴木寛治
    • Journal Title

      Organometallics 23

      Pages: 4040-4046

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Characterization of Triruthenium Complexes Containing a Perpendicularly Coordinated Alkyne Ligand2004

    • Author(s)
      高尾俊郎, 高谷輝, 室谷英介, 天神林隆一, 鈴木寛治
    • Journal Title

      Organometallics 23

      Pages: 6090-6093

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Fluxional Behavior of a Perpendicularly Coordinated μ_3-Alkyne Ligand on a Triruthenium on Cluster, Synthesis and Structure of a μ_3-η^2 : η-2(⊥)-Cycloalkyne Complex2004

    • Author(s)
      高尾俊郎, 角田 聡, 天神林隆一, 竹森利郁, 室谷英介, 鈴木寛治
    • Journal Title

      Organometallics 23

      Pages: 6094-6096

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Di-and Trinuclear Polyhydride Complexes Containing Ruthenium and Rhenium. Synthesis, Site Exchange, and H/D Exchange of Hydride Ligands2004

    • Author(s)
      J.Ito, T.Shima, H.Suzuki
    • Journal Title

      Organometallics 23

      Pages: 2447-2460

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reductive Cleavage of the N-N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex, [(Cp'Ru)3(ti-H)61X (Cp' = 775-05Me5; X = 1/2 SO4, BF4, PF6, BPh4) and Dihydrogen2004

    • Author(s)
      Y.Nakajima, A.Inagaki, H.Suzuki
    • Journal Title

      Organometallics 23

      Pages: 4040-4046

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis and Characterization of Triruthenium Complexes Containing a Perpendicularly Coordinated Alkyne Ligand2004

    • Author(s)
      T.Takao, Y.Takaya, E.Murotani, R.Tenjimbayashi, H.Suzuki
    • Journal Title

      Organometallics 23

      Pages: 6090-6093

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Fluxional Behavior of a Perpendicularly Coordinated オ3-Alkyne Ligand on a Triruthenium Cluster. Synthesis and Structure of a tirn2 : 772・ ( 1-) Cycloalkyne Complex2004

    • Author(s)
      T.Takao, S.Kakuta, R.Tenjimbayashi, T.Takemori, E.Murotani, H.Suzuki
    • Journal Title

      Organometallics 23

      Pages: 6094-6096

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Pentanuclear Polyhydride Cluster of Ruthenium with Trigonal Bipyramidal Geometry2003

    • Author(s)
      大木靖弘, 上野直樹, 鈴木寛治
    • Journal Title

      Organometallics 2

      Pages: 59-64

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Novel Trinuclear Ruthenium Polyhydride Complexes with a Triply Bridging Ligand Containing Group 1,2,12 and 13 Metals, UCp'Ru)_3(μ_3-H)'Cp'=η^3C_5Me_5; M=Li, Mg^iPr, ZnEt) and (Cp'Ru)_3(μ-M(μ-H)_3(M=AlEt and GaMe)2003

    • Author(s)
      大橋理人, 松原公紀, 飯塚 崇, 鈴木寛治
    • Journal Title

      Angew. Chem. Int. Ed. 42

      Pages: 937-940

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Nitrogen-Nitrogen Bond Cleavage of Hydrazine Drivatives by Trinuclear Pentahydride Complex of Ruthenium, (Cp'Ru)_3(μ-M(μ-H)_3(μ_3-H)_2(Cp'=η^5C_5Me_5)2003

    • Author(s)
      中島裕美子, 鈴木寛治
    • Journal Title

      Organometallics 22

      Pages: 959-969

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Bimetallic Reductive C-C Coupling Reaction Induced by Chemical Oxidation. Formation of a μ_3-C_3 Ring on Triruthenium Cluster2003

    • Author(s)
      高尾俊郎, 稲垣昭子, 室谷英介, 今村 蕾, 鈴木寛治
    • Journal Title

      Organometallics 22

      Pages: 1361-1363

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Skeletal Rearrangement in the Trinuclear nido-Ruthenecyclopentadiene Complexes. Theoretical Experimental studies2003

    • Author(s)
      稲垣昭子, D.G.Musaev, 竹森利郁, 鈴木寛治, 諸熊奎治
    • Journal Title

      Organometallics 22

      Pages: 1718-1727

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Thermal Skeletal Rearrangement of a nido-Ruthenecyclopentadiene Complexes Involving Reversible Rupture and Formation of a Ruthenium-Ruthenium Bond2003

    • Author(s)
      稲垣昭子, 高尾俊郎, 守谷 誠, 鈴木寛治
    • Journal Title

      Organometallics 22

      Pages: 2196-2198

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Versatile and Cooperative Reactivity of a Triruthenium Pentahydride Cluster. A Computational Study2003

    • Author(s)
      D.V.Khoroshun, 稲垣昭子, 鈴木寛治, S.F.Vyboishchikov, D.G.Musaev, 諸熊奎治
    • Journal Title

      J. Am. Che. Soc. 125

      Pages: 9910-9911

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis, Structures, and Reactions of Coordinatively Unsaturated Trinuclear Ruthenium Polyhydrido Complexes,[{Ru(C_5Me_5)_3(μ-H_6](y)(Y=BF_4, CF_3SO_3, 1/2(SO_4), C_6H_5CO_2, CH_3CO_2, B(C_6H_5)_4, PF6) and [{Ru(C_5Me_5)}_3(μ_3-H)_2]2003

    • Author(s)
      鈴木寛治, 柿ケ野武明, 多田賢一, 五十嵐実, 松原公紀, 稲垣昭子, 大島正人, 高尾俊郎
    • Journal Title

      Bull. Chem. Soc. Jpn. 78

      Pages: 67-87

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Pentanuclear Polyhydride Cluster of Ruthenium with Trigonal Bipyramidal Geometry2003

    • Author(s)
      Y.Ohki, N.Uehara, H.Suzuki
    • Journal Title

      Organometallics 22

      Pages: 59-64

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Trinuclear Ruthenium Polyhydride Complexes with a Triply Bridging Ligand Containing Group 1, 2, 12, and 13 Metals, (Cp'Ru)34/3-MX,u-H)3(4u3-H) (Cp' = re-05Me5; M = Li, Mg'Pr, ZnEt) and (Cp'Ru)3(y3-M)(μ-H)3 (M = AIEt and GaMe)2003

    • Author(s)
      M.Ohashi, K.Matsubara, T.Iizuka, H.Suzuki
    • Journal Title

      Angew. Chem. Mt. Ed. 42

      Pages: 937-940

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Nitrogen-Nitrogen Bond Cleavage of Hydrazine Derivatives by Trinuclear Pentahydride Complex of Ruthenium, (Cp'Ru)3(ii-H)3(23-H)2 (Cp' = ti5-05Me5)2003

    • Author(s)
      Y.Nakajima, H.Suzuki
    • Journal Title

      Organometallics 22

      Pages: 959-969

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Bimetallic Reductive C-C Coupling Reaction Induced by Chemical Oxidation. Formation of a μ3-C3 Ring on a Triruthenium Cluster2003

    • Author(s)
      T.Takao, A.Inagaki, E.Murotani, T.Imamura, H.Suzuki
    • Journal Title

      Organometallics 22

      Pages: 1361-1363

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Skeletal Rearrangement in the Trinuclear nido-Ruthenecyclopentadiene Complexes. Theoretical and Experimental Studies2003

    • Author(s)
      A.Inagaki, D.G.Musaev, T.Takemori, H.Suzuki, K.Morokuma
    • Journal Title

      Organometallics 22

      Pages: 1718-1727

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Thermal Skeletal Rearrangement of a nido-Ruthenecyclopentadiene Complex Involving Reversible Rupture and Formation of a Ruthenium-Ruthenium Bond2003

    • Author(s)
      A.Inagaki, T.Takao, M.Moriya, H.Suzuki
    • Journal Title

      Organometallics 22

      Pages: 2196-2198

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Versatile and Cooperative Reactivity of a Triruthenium Pentahydride Cluster. A Computational Study2003

    • Author(s)
      D.V.Khoroshun, A.Inagaki, H.Suzuki, S.F.Vyboishchikov, D.G.Musaev, K.Morokuma
    • Journal Title

      J. Am. Che. Soc. 125

      Pages: 9910-9911

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Migration of a Phosphine Ligand between the Two Metal Centers in Diruthenium Hydrido Complexes2002

    • Author(s)
      大木靖弘, 鈴木寛治
    • Journal Title

      Angew. Chem. Int. Ed. 41

      Pages: 2994-2997

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Rational Synthesis of Novel Tetranuclear Ruthenium Polyhydride Clusters and Their Mixed-Ligand Analogues2002

    • Author(s)
      大木靖弘, 上原直樹, 鈴木寛治
    • Journal Title

      Angew. Chem. Int. Ed. 41

      Pages: 4085-4087

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Skeletal Rearrangement of a C_2 Unit On a Triruthenium Clusters. Synthesis of μ_3-Ethyliden, and μ_3-Vinylidene Complexes by the Reaction of {Cp^*Ru(μ-H)}_3(μーH)_2 with Acetylene2002

    • Author(s)
      高尾俊郎, 竹森利郁, 守谷 誠, 鈴木寛治
    • Journal Title

      Organometallics 21

      Pages: 5190-5203

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Migration of a Phosphine Ligand between Two Meal Centers in Diruthenium Hydrido Complexes2002

    • Author(s)
      Y.Ohki, H.Suzuki
    • Journal Title

      Angew. Chem. Mt. Ed. 41

      Pages: 2994-2997

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Rational Synthesis of Novel Tetranuclear Ruthenium Polyhydrido Clusters and Their Mixed-Ligand Analogues2002

    • Author(s)
      Y.Ohki, N.Uehara, H.Suzuki
    • Journal Title

      Angew. Chem. Mt. Ed. 41

      Pages: 4085-4087

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Skeletal Rearrangement of a C2 Unit on a Triruthenium Clusters. Synthesis of /43-Ethylidene, and 3-Vinylidene Complexes by the Reaction of {CpRu(ii-H)}3(1/3-H)2 with Acetylene2002

    • Author(s)
      T.Takao, T.Takemori, M.Moriya, H.Suzuki
    • Journal Title

      Organometallics 21

      Pages: 5190-5203

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

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Published: 2008-05-27  

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