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1996 Fiscal Year Final Research Report Summary

Reactive Organometallics of Transition Metals

Research Project

Project/Area Number 05236104
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionOsaka University

Principal Investigator

MURAHASHI Shun-ichi  Osaka University, Graduate School of Engineering Science, Professor, 大学院・基礎工学研究科, 教授 (60029436)

Co-Investigator(Kenkyū-buntansha) YASUDA Hajime  Hiroshima University, Faculty of Engineering, Professor, 工学部, 教授 (00028200)
TAKAHASHI Shigetoshi  Osaka University, The Institute of Scientific and Industrial Research, Professor, 産業科学研究所, 教授 (70029875)
SUZUKI Hiroharu  Tokyo Institute of Technology, Faculty of Engineering, Professor, 工学部, 教授 (30106629)
KUWAJIMA Isao  Tokyo Institute of Technology, Faculty of Science, Professor, 理学部, 教授 (50016086)
ITO Takashi  Yokohama National University, Faculty of Engineering, Professor, 工学部, 教授 (50016721)
Project Period (FY) 1993 – 1996
KeywordsRedox Lewis acid / Redox Lewis base / Ruthenium polyhydride / Lanthanide / Molybdenum polyhydride / C-H Activation / Polymerization / Vinyl sulfide
Research Abstract

Aiming to acquire innovative method of chemical transformation for the future, the research group designed and prepared reactive organometallics of transition metals, and their functions as reagents and catalysts have been investigated. The representative results are as follows. Low valent transition metal polyhydrides have proven to act as either redox Lewis acid or base catalysts by their specific ability to activate of alpha-C-H and CN bonds of nitriles. The principle has led to development of a variety of novel catalytic reactions such as aldol condensation, Michael addition, and transformations of CN functionalities with nucleophiles which proceed under neutral conditions (Murahashi). Lanthanide organometallics bearing bulky metallocenes were found to show high activity for polymerization of ethylene and methacrylates. The corresponding polymers have been obtained with high molecular weight, high syndiotacticity, and narrow polydispencity (Yasuda). A series of polyhydrido organome … More tallics of group 6 transition metals have been prepared. The coordinatively unsaturated active species have been created by light irradiation, and their reactivities towards oxidative addition to organic substrates such as alcohols and amides have been investigated (Ito). The active catalytic species derived from the reaction of vinyl sulfides with Lewis acids have proven to be versatile synthetic intermediates for construction of carbon skeletons using ene reactions, [3+2] cycloaddition and ring closing coupling reactions (Kuwajima). Novel trinuclear ruthenium complexes bearing bridging polyhydrido ligands have been created, and these complexes show specific reactivity towards carbon-carbon bond cleavage and C-H activation of cyclopentadiene via multimetallic cooperation (Suzuki). Bimetallic platinum-palladium organometallics bearing mu-ethynediyl ligands have been prepared. High catalytic activity towards living polymerization of aryl isocyanides was observed with these unique complexes (Takahashi). Less

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] S.-I.Murahashi: "Ruthenium-Catalyzed Oxidation of Phenols with Alky1 Hydroperoxides.A Noves,Facile Route to 2-Substituted Ouinones" J.Am.Chem.Soc. 118. 2509-2510 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Ito: "Synthesis,Structures,and Reactions of Di-μ-hydroxo Dinuclear Complexes of Tungsten(IV)and Molybdenum(IV)" Organometallics. 15. 852-859 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Kuwajima: "A New Synthetic Method for Cyclopentanones via Formal [3+2] Cycloaddition Reaction" Synlett. 157-158 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Suzuki: "Novel Dinuclear μ-Hydrido-μ-methyleneamidoruthenium Complexes,[(η^5-C_5Me_5)Ru]_2(μ-H)(μ-N=CHR)(μ-L)(R=Me,Et;L=MeCN,arene),as Precursors of Active Species for Bimetallic Activation." Organometallics. 15. 2422-2424 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Takahashi: "Screw-Sense-Selective Polymerization of Isocyanides by Dinuclear μ-Ethynediyl Complexes" Angew.Chem.,Int.Ed.Engl.35. 1554-1556 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Yasuda: "Biodegradation of Novel Optically Active Polyesters Synthesized by Copolymerization of (R)-MOHEL with Lactones" Macromolecules. 29. 4821-4829 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-I.Murahashi: "Ruthenium-Catalyzed Oxidation of Phenols with Alkyl Hydroperoxides. A Novel, Facile Route to 2-Substituted Quinones" J.Am.Chem.Soc.118. 2509-2510 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ito: "Synthesis, Structures, and Reactions of Di-mu-hydroxo Dinuclear Complexes of Tungsten (IV) and Molybdenum (IV)" Organometallics. 15. 852-859 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I.Kuwajima: "A New Synthetic Method for Cyclopentanones via Formal [3 + 2] Cycloaddition Reaction" Synlett. 157 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Suzuki: "Novel Dinuclear mu-Hydrido-mu-methyleneamidoruthenium Complexes, [(eta^5-C_5Me_5)Ru]_2 (mu-H) (mu-N=CHR) (mu-L) (R = Me, Et ; L = MeCN,arene), as Precursors of Active Species for Bimetallic Activation. Dehydrogenative Coupling of Ethylene on Dinuclear Complex" Organometallics. 15. 2422-2424 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Takahashi: "Screw-Sense-Selective Polymerization of Isocyanides by Dinuclear mu-Ethynediyl Complexes" Angew.Chem., Int.Ed.Engl.35. 1554-1556 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Yasuda: "Biodegradation of Novel Optically Active Polyesters Synthesized by Copolymerization of (R) -MOHEL with Lactones" Macromolecules. 29. 4821-4829 (1996)

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

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Published: 1999-03-09  

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