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New Transformations of Unsaturated Hydrocarbons with Polynuclear Complexes of Pd (I)

Research Project

Project/Area Number 11490023
Research Category

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

Allocation TypeSingle-year Grants
Section一般
Research Field 広領域
Research InstitutionOsaka University

Principal Investigator

KUROSAWA Hideo  Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (40029343)

Co-Investigator(Kenkyū-buntansha) MURAHASHI Tetsuro  Osaka University, Graduate School of Engineering, Assistant, 大学院・工学研究科, 助手 (40314380)
OGOSHI Sensuke  Osaka University, Graduate School of Engineering, Lecturer, 大学院・工学研究科, 講師 (30252589)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2000: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsPd (I) Complex / Sandwich complex / Bridge complex / 袈橋配位子 / 親電子攻撃 / アルキン2量化
Research Abstract

Increasing attention has been paid to rapid progress in the field of organic synthesis by means of palladium complex based catalyst. In most of the catalysis, key intermediates are believed to have the oxidation state of Pd (0) and Pd(II). However, there is an urgent need to revolutionize this methodology. The aim of the present project is to lay a molecular level basis for the synthetic method of the next generation by studying preparation, structure and reactions of polynuclear Pd (I) complexes containing bridging ligands such as allyl, propargyl, vinyl, alkynyl, and carbene. First of all, the Pd (I)-Pd (I) complexes containing 4 and 6 acetonitrile ligands, which can readily be replaced by weak ligands such as unsaturated hydrocarbons, have been prepared. X-ray structure determination established coordination of two PPh_3 ligands to the Pd (I)-Pd (I) unit having four acetonitrile ligands. This complex reacted with two equiv. phenylacetylene to give the Pd-Pd complex containing the bridging butenediylidene ligand made by head-to-tail dimerization of the acetylene. The Pd (I)-Pd (I) complex having six acetonitrile ligands reacted with 1, 8-diphenyloctatetraene in the presence of Pd (0) complex to give novel sandwich complex made by two tetraen ligands coordinating to the linear Pd_4 chain. Next the Pd (I)-Pd (I) complexes containing bridging diene and allene ligands were synthesized, and their structures determined by NMR and X-ray analysis as well as by MO calculation. These studies established that considerable electron density flows from the Pd-Pd σ orbital to the antibonding MO of the organic ligand through back bonding interaction.

Report

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

    (12 results)

All Other

All Publications (12 results)

  • [Publications] T.Murahashi,E.Mochizuki,Y.Kai,H.Kurosawa: "Organometallic Sandwich Chains Mede of Conjugated Polyenes and Metal-metal Chains"J.Am.Chem.Soc.. 121. 10660-10661 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi,T.Otani,T.Okuno,H.Kurosawa: "Coupling of Alkynes on Pd-Pd to Generate an Electrophilic μ-Butenediylidene Moiety"Angew.Chem.Int.Ed.Engl.. 39. 537-540 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi,T.Nagai,T.Okuno,T.Matatani,H.Kurosawa: "Synthesis and Ligand Substitution Reaction of Homoleptic Acetonitrile Dipalladium (I) Complex"J.Chem.Soc.Chem.Comm.. 1689-1690 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Ogoshi,T.Nishida,K.Tsutsumi,M.Oi,H.Kurosawa: "Carbon-carbon Bond Formation by Electrophilic Addition at Central Carbon of μ-η^3-Allenyl/propargyl Ligand on Pd-Pd Bond"J.Am.Chem.Soc.. 123(印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi, E.Mochizuki, Y.Kai, H.Kurosawa: "Organometallic Sandwich Chains Made of Conjugated Polyenes and Metal-Metal Chains"J.Am.Chem.Soc.. 121. 10660-10661 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi, T.Otani, T.Okuno, H.Kurosawa: "Coupling of Alkynes on Pd-Pd to Generate an Electrophilic μ-Butendiylidene Moiety."Angew.Chem.Int.Ed.Engl.. 39. 537-540 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi, T.Nagai, T.Okuno, T.Matsutani, H.Kurosawa: "Synthesis and Ligand Substitution Reaction of Homoleptic Acetonitrile Dipalladium (I) Complex."J.Chem.Soc., Chem, Comm.. 1689-1690 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Ogoshi, T.Nishida, K.Tsutsumi, M.Ooi, H.Kurosawa: "Carbon-Carbon Bond Formation by Electrophilic Addition at Central Carbon of μ-η^3-Allenyl/propargyl Ligand on Pd-Pd Bond."J.Am.Chem.Soc.. 123 (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Murahashi,T.Nagai,T.Okuno,T.Matsutani,H.Kurosawa: "Synthesis and Ligand Substitution Reaction of Homoleptic Acetonitrile Dipalladium (1) Complex"J.Chem.Soc.Chem.Comm.. 1689-1690 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Ogoshi,T.Nishida,K.Tsutsusmi,M.Doi,H.Kurosawa: "Carbon-Carbon Bond Formation by Electrophilic Addition at the Central Carbon of the -3-Allenyl/Propargyl Ligand on the Pd-Pd Bond"J.Am.Chem.Soc.. 123(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Murahashi,E.Mochizuki,Y.Kai,H.Kurosawa: "Organometallic Sandwich Chains Made of Conjugated Polyenes and Metal-Metal Chains"J.Am.Chem.Soc.,. 121. 10660-10661 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Murahashi,T.Otani,T.Okuno,H.Kurosawa: "Coupling of Alkynes on pd-pd to Generate an Electrophilic μ-Butenediylidene Moiety"Angew.Chem.Int.Ed.. 39. 537-540 (2000)

    • Related Report
      1999 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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