• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Preparation and Control of Coordinatively Unsaturated Active Species

Research Project

Project/Area Number 63470078
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

TAKAHASHI Tamotsu (1989)  The University of Tokyo, Faculty of Engineering, Department of Industrial Chemistry, Research Associate, 工学部, 助手 (30163273)

内田 安三 (1988)  東京大学, 工学部, 教授 (00010752)

Co-Investigator(Kenkyū-buntansha) UCHIDA Yasuzo  Nagaoka University of Technology, Vicepresident, 副学長 (00010752)
SABURI Masahiko  The University of Tokyo, Faculty of Engineering, Department of Synthetic Chemist, 工学部, 助教授 (90011022)
高橋 保  東京大学, 工学部, 助手 (30163273)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1989: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1988: ¥4,700,000 (Direct Cost: ¥4,700,000)
KeywordsFive Coordinate Ru Complex / Molecular Hydrogen Complex / Agostic Interaction / Carbon-carbon Bond Formation / Zirconium-olefin Complex / Carbon-carbon Bond Activation
Research Abstract

Five coordinate ruthenium complexes [RuH(P-P)_2]PF_6 were prepared with various phosphines such as dppe, dppp, dpppb,diop, dppf, binap, where dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, dppb is 1,4-bis(diphenylphosphino)-propane, diop is 2,3-o-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, dppf is 1,2-bis(diphenylphosphino)ferrocene, binap is 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. The NMR studies of these complexes indicated that they have a 6th ligand such as solvent, nitrogen molecule and so on, in solution. When complexes have large chelate rings with phosphines, observed were predominant formation of cis isomers with agostic interactions with phenyl group of phosphines. Further investigations with dppb under argon, nitrogen or hydrogen atmosphere revealed that this agostic interaction was stronger than the coordination of nitrogen molecule or solvent, and weaker than molecular hydrogen coordination. The structure of dpp … More f-complex was determined by x-ray study, indicating the cis-structure due to the steric hindrance of dppf. Hydrogen molecule coordinated to this complex to give novel type of molecular hydrogen complex. T_1 value of H_2 ligand of this complex showed that the H_2 and original hydride ligands are equivalent, in other word, this was a trihydride complex.
In the case of zirconium species, we found the followings. The active species quantitatively formed from zirconocenedialkyls were zirconocene(II) olefin complexes. The structure of zirconocenestilbene complex was determined by x-ray analysis. Reactions of zirconocene olefin complexes with another olefins gave olefin-olefin cross coupling products with >99% of regio-selectivities and >99% of stereo-selectivities. In addition the detail investigations of its mechanism led the development: of novel skeleton rearrangement by carbon-carbon bond activation in the case of zircona- or hafnacyclopentane derivatives. Methyl group of alpha-position could be transferred to beta-position selectively by this novel method. Less

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] M.Saburi,K.Aoyagi,T.Takahashi,Y.Uchida: "Chelate Size Dependence of Dihydrogen-Hydride Exchange Ruthenium(II)Molecular Hydrogen Complexes with Diphos-phines[RuH(η^2-H_2)(P-P)_2]+(P-P)=Ph_2P(CH_2)_nPPH_2:n=2,3,4" Chem.Lett.,in press.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Takahashi,M.Murakami,M.Kunishige,M.Saburi,Y.Uchida,K.Kozawa,T.Uchida et al.: "Zirconocene-alkene Complexes.An X-Ray Structure and a Novel Preparative Method." Chem.Lett.,. 761-764 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] D.R.Swanson,C.R.Rousset,E.Negishi,T.Takahashi,T.Seki,M.Saburi,and Y.Uchida: "Regio-and Diastereoselective Alkyl-alkene and Alkene-alkene Coupling Promoted by Zirconocene and Hafnocene" J.Org.Chem.,. 54. 3521-3523 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Takahashi,M.Tamura,M.Saburi,Y.Uchida,E.Negishi: "Preparation of Hafnocene-Ethylene COmplex from Bis(η^5-cyclopentadienyl)hafnacyclopentane and its Characterization" J.Chem.Soc.,Chem.Commun.,. 852-853 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Takahashi,T.Fujimori,T.Seki,M.Saburi,Y.Uchida,C.R.Rousset,E.Negishi: "Selective Skeltal Rearrangement by Carbon-carbon Bond Activation" J.Chem.Soc.,Chem.Commun.,in press.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Takahashi: "Selective Molecular Transformation by Carbon-carbon Bond Activation" 有機合成協会誌(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Saburi, K. Aoyagi, T. Takahashi, and Y. Uchida: "Chelate Size Dependence of Dihydrogen-Hydride Exchange Ruthenium(II) Molecular Hydrogen Complexes with Diphosphines [RuH(eta^2-H_2)(P-P)_2]^+ (P-P) = Ph_2P(CH_2)_nPPh_2: n = 2, 3, 4" Chem. Lett., in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Takahashi, M. Murakami, M. Kunishige, M. Saburi, Y. Uchida, K. Kozawa, T. Uchida et al.: "Zirconocene-alkene Complexes. An X-Ray Structure and a Novel Preparative Method" Chem. Lett., 761-764, (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] D.R. Swanson, C.R. Rousset, E. Negishi, T. Takahashi, T. Seki, M Saburi, and Y. Uchida: "Regio- and Diastereoselective Alkyl-alkene and Alkene-alkene Coupling Promoted by Zirconocene and Hafnocene" J. Org. Chem., 54, 3521-3523 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Takahashi, M. Tamura, M. Saburi, Y. Uchida, and E. Negishi: "Preparation of Hafnocene-Ethylene Complex from Bis-(eta^5-cyclopentadienyl)hafnacyclopentane and its Characterization" J. Chem Soc., Chem. Commun., 852-853 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Takahashi, T. Fujimori, T. Seki, M. Saburi, Y. Uchida, C.R.Rousset, and E. Negishi: "Selective Skeletal Rearrangement by Carbon-carbon Bond Activation" J. Chem. Soc., Chem. Commun.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Takahashi: "Selective Molecular Transformation by Carbon-carbon Bond Activation" Yuki Gosei Kyokai-shi.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Saburi,K.Aoyagi,T.Takahashi,Y.Uchida: "Chelate Size Dependence of Dihydrogen-Hydride Exchange Ruthenium(II)Molecular Hydrogen Complexes with Diphosphines〔RuH(n^2-H_2)(P-P)_2〕+(P-P)=Ph_2P(CH_2)_nPPh_2:n=2,3,4" Chem.Lett.,in press.

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Takahashi,M.Murakami,M.Kunishige,M.Saburi,Y.Uchida,K.kozawa,T.Uchida et al.: "Zirconocene-alkene Complexes. An X-Ray Structure and a Novel Preparative Method." Chem.Lett.,. 761-764 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] D.R.Swanson,C.R.Rousset,E.Negishi,T.Takahashi,T.Seki,M.Saburi,and Y.Uchida: "Regio-and Diastereoselective Alkyl-alkene and Alkene-alkene Coupling Promoted by Zirconocene and Hafnocene" J.Org.Chem.,. 54. 3521-3523 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Takahashi,M.Tamura,M.Saburi,Y.Uchida,E.Negishi: "Preparation of Hafnocene-Ethylene Complex from Bis(n^5-cyclopentadienyl)hafnacyclopentane and its Characterization" J.Chem.Soc.,Chem.Commun.,. 852-853 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Takahashi,T.Fujimori,T.Seki,M.Saburi,Y.Uchida,C.R.Rousset,E.Negishi: "Selective Skeltal Rearrangement by Carbon-carbon Bond Activation" J.Chem.Soc.,Chem.Commun.,.

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Takahashi: "Selective Molecular Transformation by Carbon-carbon Bond Activation" 有機合成協会誌.

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Takahishi,M.Murakami,M.Kunishige,M.Saburi.Y.Uchida,K.Kozawa,T.Uchida,D.R.Swanson,E.Negishi: Chem.Lett.

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Takahashi,M.Tamura,M.Saburi,Y.Uchida,E.Negishi: J.Chem.Soc.Chem.Commun.

    • Related Report
      1988 Annual Research Report

URL: 

Published: 1988-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi