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Reactions of Metal-Metal-Bonded Binuclear Complexes

Research Project

Project/Area Number 59470036
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionOsaka City University

Principal Investigator

NAKAMURA Yukio  Department of Chemistry, Faculty of Science, Osaka City University, 理学部, 助教授 (20047012)

Co-Investigator(Kenkyū-buntansha) ISOBE Kiyoshi  Department of Chemistry, Faculty of Science, Osaka City University, 理学部, 講師 (70101285)
Project Period (FY) 1984 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1986: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1985: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1984: ¥5,100,000 (Direct Cost: ¥5,100,000)
KeywordsMetal-Metal Bonds / Diphosphine Complexes / Model-Enzyme / Photochemical Reaction / Heterobinuclear Complexes / <mu> -Xylylene Complexes / μ-メチレン錯体
Research Abstract

1. Reactions of M <(acac)_2> (M=Pd,Pt) with dppm(= <Ph_2> <PCH_2> <PPh_2> ) to from M <(dppm-H)_2> (dppm-H=a deprotonated dppm anion) and methylation of the carbanions in Pt <(dppm-H)_2> with MeI have been studied, and both the reaction schemes were elucidated with the aim of <^1H> , <^(13)C> , or <^(31)P> NMR spectroscopy.
2. Reactions of <[Pd(dppm)_2]^(2+)> with <[CpMo(CO)_3]^-> as a nucleophile was examined to obtain a certain heterobimetallic complex and the desired complex [ <(CO)_3> Mo <((mu)-dppm)_2> -PdCp] ( <PF_6> ) was synthesized and characterized. 3. Photochemical reactions of <[CpMo(CO)_3]_2> with <NO(_2^-)> or dark reactions of <[CpMo(CO)_2]_2> with <NO(_2^-)> and <NO(_3^-)> have been elucidated to give the mononuclear complex [CpMo <(CO)_2> (NO)], and the reaction mechanism was also proposed.
4. The nucleophilic attak of <[CpMo(CO)_3^-> at the benzyl carbons of <alpha> , <alpha> ' -dibromo-o, m, p-xylene was found to afford <mu> -xylylene complexes which react with <PMe_2> Ph to give acyl complexes. It was revealed that photo-irradiation of the <mu> -xylylene complexes induce homolytic cleavage of the Mo-C bond.
5. The redox behavior of <[Rh(C_5Me_5)Me]_2> <(mu)-CH_2)_2> were examined by cyclic voltammetry and the presence of three oxidation waves were recognized. A possible scheme on the oxidation was proposed based on the following experimental data: controlled potential electrolysis, analysis of the evolved gases, and ESR measurement of the electrolyzed solution.

Report

(1 results)
  • 1986 Final Research Report Summary
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Kiyoshi ISOBE: Journal of the Chemical Society,Chemical Communications. 378-380 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: Inorganica Chimica Acta. 120. L25-L26 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: Inorganica Chimica Acta. 122. L9-L11 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: Journal of Organometallic Chemistry.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: Journal of Organometallic Chemistry.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: Inorganica Chimica Acta.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: Bulletin of the Chemical Society of Japan.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: Bulletin of the Chemical Society of Japan.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: "Photochemical Reactions of [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_6> ](Mo-Mo) and Dark Reactions of [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_4> ](Mo-Mo) with <NaNO_2> and <NaNO_3> : Reduction of <NO(_2^-)> and <NO(_3^-)> to Coordinated NO." Journal of the Chemical Society, Chemical Communications. 378-380 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: "Facile Deprotonation of Coordinated Bis(diphenylphosphino)methane by an Acetylacetonate Anion." Inorganica Chimica Acta. 120. L25-L26 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: "Consecutive Methylation and Protonation of the Carbanions in [Pt <(Ph_2PCHPPh_2)_2> ] Giving Rise to Ligand Scrambling." Inorganica Chimica Acta. 122. L9-L11 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: "Comparative Studies of the Photochemical and Thermal Reactivities of the Molybdenum-Molybdemum Single Bond in [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_6> ] and Triple Bond in [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_4> ] towards Nirite and Nitrate." Journal of Organometallic Chemistry.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: "Synthesis and Photochemical Behavior of <mu> -p-Xylylene Dimolybdemum( <II> ) Complexes." Journal of Organometallic Chemistry.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: "Reactions of Bis(beta-diketonato)platinum( <II> ) and -palladium( <II> ) with Diphosphines <Ph_2> <PCHRPPh_2> (R=H,Me) : Unexpected Formation of the Homoleptic Bis(diphenylphosphino)methanido and Related Complexes." Inorganica Chimica Acta.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Hiromasa HASHIMOTO: "Novel Ligand Scrambling Reactions Caused by the Methylation and Protonation of the Carbanions in Bis(diphenylphosphino)methanido Complex of Platinum( <II> )." Bulletin of the Chemical Society of Japan.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Kiyoshi ISOBE: "Electrochemical Coupling Reactions of Four <C_1> Ligands in <[Cp^*Rh(CH_3)]_2> <((mu)-CH_2)_2> ." Bulletin of the Chemical Society of Japan.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary

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Published: 1987-03-31   Modified: 2016-04-21  

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