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1992 Fiscal Year Final Research Report Summary

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
KeywordsDinitrogen / Catalysis Silylamine / Silylation / Germylation / Silyldiazenido / Silylhydrazido
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.

  • Research Products

    (10 results)

All Other

All Publications (10 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 1994-03-24  

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