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Study on the syntheses of Silyldiazanes from Molecular Nitrogen and the Application of Silydiazenes as Redical Precursors

Research Project

Project/Area Number 61850149
Research Category

Grant-in-Aid for Developmental Scientific Research

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionUniversity of Tokyo

Principal Investigator

HIDAI Masanobu  Faculty of Engineering, University of Tokyo, 工学部, 教授 (60011011)

Co-Investigator(Kenkyū-buntansha) MIZOBE Yasushi  Faculty of Engineering, University of Tokyo, 工学部, 助手 (40175609)
Project Period (FY) 1986 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1987: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1986: ¥2,400,000 (Direct Cost: ¥2,400,000)
KeywordsSilyldiazene / Silysiazenido complex / Silylhydrazido complex / 触媒的シリルアミン合成 / 窒素錯体 / トリメチルシリル化反応 / ジアゼニド錯体 / ヒドラジド錯体
Research Abstract

When treated with Me_3 SiI of CF_3SO_3SiMe_3 in benzene, a series of dinitrogen complexes (M(N_2)_22(L)_4) (M = W, Mo: L = tertiary phosphine) afforded trimethlsilyldiazenido (MNNSiME_3) andteimethylsilyihydrazido(2-) (MNNHSiMe_3) complexes under mild conditions. The former compiexes well correspond to the intermediate stage from molecular nitrogen toward silyldiazanes, although we have not yet succeeded in the conversion of the silyldiasinido groups into silyldiazenes. On the other hand, we have recently found that treatment of Me_3SiCl with Na dispersion if THF at 30゜c under atmospheric pressure of N_2 gives N(SiMen13n2)_3 and HN(SiMe_3)_2 in the presence of cis-(Mo(N_2)_2(PMe_2Ph)_4). The formation of silylamines is catalytic and the maximum yield observed till now is 38% based on Me_<23>SiCl chatged, which correspones to the turnover number of 25 based on the molybdenum. The catalytic activity of the tungsten analogue was much lower than that of the molybdenum complex under the same reaction conditions.

Report

(2 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (8 results)

All Other

All Publications (8 results)

  • [Publications] Keiko Orisaku: Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Keiko Orisaku: J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 千鯛眞信: 科学. 57. 157-163 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Masanobu Hidai: "Molybdenum Enzymes" John Wiley & Sons,Inc., 56 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Masanobu Hidai: "Reactions of Coordinated Ligands (in press)" Plenum Press,

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Masanobu Hidai: "Kagaku (Science)" Recent Development in Nitrogen Fixation (Japanese). 57. 157-163 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Keiko Orisaku: "Syntheses and Some Reactions of Trimethylsilylated Dinitrogen Complexes of Tungsten and Molybdenum" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Keiko Orisaku: "Catalytic Formation of silylamines from Silyly Chloride, Sodium and Molecular Nitrogen Promoted by Molybdenum Complexes" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary

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

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