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Silylation of Dinitrogen Coordinated to Transition Metals and its Application to Catalytic Nitrogen Fixation

Research Project

Project/Area Number 03453097
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

HIDAI Masanobu  Univ. of Tokyo, Fac. of Eng. Professor, 工学部, 教授 (60011011)

Co-Investigator(Kenkyū-buntansha) MIZOBE Yasushi  Univ. of Tokyo, Fac. of Eng. Lecturer, 工学部, 講師 (40175609)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥6,900,000 (Direct Cost: ¥6,900,000)
Fiscal Year 1992: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1991: ¥4,600,000 (Direct Cost: ¥4,600,000)
KeywordsDinitrogen / Catalysis Silylamine / Silylation / Germylation / Silyldiazenido / Silylhydrazido / タングステン窒素錯体 / モリブデン窒素錯体 / 配位窒素シリル化反応 / シリルアミン
Research Abstract

1. Treatment of a dinitrogen complex cis-[W(N_2)_2(PMe_2Ph)_4](1a) with R_3SiCl/NaI mixtures afforded a variety of silyldiazenido complexed trans-[WI(NNSiR_3)(PMe_2Ph)_4], while the reactions of 1a or its Mo analogue 1b with ClSiMe_2CH_2CH_2SiMe_2Cl/NaI resulted in the formation of silylhydrazido(2-) complexes cis, mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3](2). Complex 1a also reacted with R_3GeCl/NaI to give germyldiazenido complexes trans-[WI(NNGeR_3)(PMe_2Ph)_4].
2. By treatment with R_3SiCl and Na in the presence of a catalytic amount of 1b, molecular nitrogen has been converted into silylamines under ambient conditions. The yields of silylamines produced by these novel catalytic reactions considerably depended upon the nature of the substituents attached to the Si atom.
3. One PMe_2Ph ligand in 2 was replaced readily by a series of pi-acceptor ligands at room temperature, affording various disilylhydrazido(2-) complexes cis, trans-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2(L)](L = CO, CH_2=CH_2, RCN). In contrast, from the reaction mixture of 2 with 'BuNC a cationic complex mer-[WI(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]I has been isolated as the major product. Furthermore, 2 reacted with CH_2X_2 (X = I, Cl) to give paramagnetic W(V) complexes mer, trans-[WX_3(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2]. Hydrolysis of this W(V) complex (X = I) and the subsequent condensation reaction with ketones afforded new W(V) complexes [WI_3(NNH_2)(PMe_2Ph)_2] and mer, trans-[WI_3(NN=CRR')(PMe_2Ph)_2], respectively.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] H.Oshita: "Novel Disilylation of Dinitrogen Ligand in csi-[W(N_2)_2(PMe_2Ph)_4].Synthesis and Reactivity of mer-[Wl_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]" Organometallics. 11. 4116-4123 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Oshita: "Silylation and Germylation of a Coordinated Dinitrogen in csi-[M(N_2)_2(PMe_2Ph)_4] (M=Mo,W)Using R_3ECl/NaI and R_3ECl/Na Mixtures (E=Si,Ge)" J.Organomet.Chem.(1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Oshita: "Preparation and Characterization of Paramagnetic W(V) Diazoalkane Complexes mer,trans-[WX_3(NN=CMeR)(PMe_2Ph)_2] (X=Br,I;R=Me,Ph)and Hydrazido(2-) Complex [Wl_3(NNH_2)(PMe_2Ph)_2]." J.Organomet.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 溝部 裕司: "前周期遷移金属の有機化学" 日本化学会編 学会出版センター, (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Hidai: "Molybdenum Enzymes,Cofactors and Model-Systems" E.I.Stiefel,D.Coucouvanis,and W.E.Newton,Eds.,American Chemical Society, (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H. Oshita: "Novel Disilylation of Dinitrogen Ligand in cis-[W(N_2)_2(PMe_2Ph)_4]. Synthesis and Reactivity of mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]" Organometallics. 11. 4116-4123 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H. Oshita: "Silylation and Germylation of a Coordinated Dinitrogen in cis-[M(N_2)_2(PMe_2Ph)_4] (M = Mo, W) Using R_3ECl/NaI and R_3ECl/Na Mixtures (E = Si, Ge)" J. Organomet. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H. Oshita: "Preparation and Characterization of Paramagnetic W(V) Diazoalkane Complexes mer, trans-[WX_3(NN=CMeR)(PMe_2Ph)_2] (X = Br, I; R = Me, Ph) and Hydrazido(2-) Complex [WI_3(NNH_2)(PMe_2Ph)_2]" J. Organomet. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M. Hidai: "Molybdenum Enzymes Cofactors and Model Systems" American Chemical Society.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Mizobe: "Organic Chemistry of Early Transition Metals" Gakkai Shuppan Center.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Oshita: "Novel Disilylation of Dinitrogen Ligand in cis-[W(N_2)_2(PMe_2Ph)_4.Synthesis and Reactivity of mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3" Organometallics. 11. 4116-4123 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Oshita: "Silylation and Germylation of a Coordinated Dinitrogen in cis-[M(N_2)_2(PMe_2Ph)_4](M=Mo,W)Using R_3ECl/NaI and R_3ECl/Na Mixtures(E=Si,Ge)" J.Organomet.Chem.(1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] 溝部 裕司: "前周期遷移金属の有機化学" 日本化学会編学会出版センター, (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Hidai: "Molybdenum Enzymes,Cofactors and Model Systems" E.I.Stiefel,D.Coucouvanis,and W.E.Newton,Eds.,American Chemical Society, (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Andrew C.Street: "Silylation of Coordinated Dinitrogen by Silylcobalt Complexes.Preparation of a New Series of Silyldiazenido and Silylhydrazido(2ー) Complexes of Molybdenum and Tungsten" Chem.Lett.383-386 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hiroyuki Oshita: "Disilylation of Coordinated Dinitrogen in cisー[W(N_2)_2(PMe_2Ph)_4] to Give Disilylhydrazido(2ー) Complex merー[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]." Inorg.Chem.

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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