• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of New Chemical Nitrogen Fixation.

Research Project

Project/Area Number 13450366
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionTokyo University of Science

Principal Investigator

HIDAI Masanobu  Tokyo University of Science, Faculty of hidustrial Science and Technology, Professor, 基礎工学部, 教授 (60011011)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥14,200,000 (Direct Cost: ¥14,200,000)
Fiscal Year 2003: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2002: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2001: ¥5,400,000 (Direct Cost: ¥5,400,000)
KeywordsDinitrogen / Dihydrogen / Ammonia / Amido-Complex / Cuban-type Cluster / Ruthenium / ジアミド / チオエーテル配位子 / ジアミド-チオエーテル配位子
Research Abstract

Recently we have found the novel reaction of a tungsten dinitrogen complex with acidic ruthenium η^2-dihydrogen complexes to form ammonia under mild conditions, although the reaction is stoichiometric.
In this project, we have paid our attention to late transition metal complexes by which both dinitrogen and dihydrogen are bound and activated.Our purpose is to develop the nitrogen fixation catalytic cycle in which dihydrogen is used for protonation and reduction of the coordinated dinitrogen on a metal complex. We have investigated synthesis and reactivity of late transition-metal complexes containing tridentate diamidoAbloether(NSN-type), diamido/phosphine(NPN-type), and diamido/amine(NNNAype)ligands.Although dinitrogen complexes could not be isolated, the IR spectrum-of a reaction solution showed the formation of [Ru(NSN)(PMe_3)_2(N≡N)], but hydrogenation of dinitrogen did not proceed.However, we have found the catalytic hydrogenation of benzonitnle, an isoelectronic molecule of dinit … More rogen, by employing those metal complexes containing tridentate amido ligands.
On the other hand, the chemistry of multimetallic sulfido clusters has been receiving much attention in relevance to the active sites of nitrogenase. We have long aimed at construction of polynuclear metal-sulfur reaction sites, the stnictures of which are carefully controlled at molecular levels.In this study, cubane-type clusters having a [Mo_3MS_4] (M=Ru, Rh, Ni, Pd, Pt)core were prepared and their reactivities were investigated.The disproportionation reaction of hydrazine proceeded to form ammonia and dinitrogen, when [(Cp^^*Mo)_3(η^3-S)_4RuH_2(PAr_3)](Ar=Ph, p-tolyl)was reacted with hydrazine.Although attempts to prepare[Mo_3RuS_4]clusters binding dinitrogen on ruthenium have failed, [Mo_3NiS_4]clusters showed novel catalytic activity for the cyclization of alkynoic acids to enol lactones, which was not catalyzed by mononuclear Ni complexes.Further, [Mo_3MS_4](M=Pd, Ru)clusters exhibited higher catalytic activity than mononuclear Pd or Ru complexes for the intramolecular hydroamination of aminoalkynes. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (36 results)

All Other

All Publications (36 results)

  • [Publications] Kuwata S.: "Hydrosuifido Complexes of Transition Metals"Coord.Chem.Rev.. 213. 211-305 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Chemical Nitrogen Fixation by Using Molybdenum and Tungsten Complexes"Pure Appl.Chem.. 73. 261-263 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Seino, H.: "Transformation of Organic Molecules on the Low-Valent {M(Ph_2PCH_2CH_2PPh_2)_2}Moiety Derived from trans-[M(N_2)_2(Ph_2PCH_2CH_2PPh_2)_2]or Related Complexes (M=Mo,W)"Chem.Rec.. 1. 349-361 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takemoto, S.: "Ruthenium Complexes Containing Bis(diarylamido)/Thioether Ligands : Synthesis and Their Catalysis for the Hydrogenation of Benzonitrile"Organometallics. 21・19. 3897-3904 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takei, I.: "Synthesis of a New Family of Heterobimetallic Tetranuclear Sulfido Clusters with Mo_2Ni_2S_x(x=4 or 5)or Mo_3M'S_4(M'=Ru,Ni,Pd) Cores"Organometallics. 22・9. 1790-1792 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takei, I.: "Synthesis of Cubane-Type Mo_3M'S_4 Clusters and Their Catalytic Activity for the Cyclization of Alkynoic Acids to Enol Lactones"Organometallics. 22・23. 4639-4641 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Recent Advances in Hydride Chemistry"Elsevier Science B.V.. 22 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Molybdenum and Tungsten. Their Roles in Biological Processes(Metal Ions in Biological Systems, Vol 39)"41 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Encyclopedia of Catalysis"John Wiley & Sons, Inc. 8 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Modern Coordination Chemistry : The Legacy of Joseph Chatt"The Royal Society of Chemistry. 9 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Perspectives in Organometallic Chemistry"The Royal Society of Chemistry. 12 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kuwata S., Hidai, M.: "Hydrosulfido Complexes of Transition Metals"Goord.Chem.Rev.. 213. 211-305 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M., Mizobe, Y.: "Chemical Niirogen Fixation by Using Molybdenum and Tungsten Complexes"Pure Appl.Chem.. 73. 261-263 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Seino, H., Mizobe, Y., Hidai, M.: "Transformation of Organic Molecules on the Low-Valent{M(Ph_2PCH_2CH_2PPh_2)_2} Moiety Derived from trans-[M(N_2)_2(Ph_2PCH_2CH_2PPh_2)_2]or Related Complexes(M=Mo, W)"Chem.Rec.. 1. 349-361 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takemoto, S., Kawamura, H., Yamada, Y., Okada, T., Ono, A., Yoshikawa, E., Mizobe, Y., Hidai, M.: "Ruthenium Complexes Containing Bis(diarylamido)/Thioether Ligands : Synthesis arid Their Catalysis for the Hydrogenation of Benzonitrile"Organometailics. 21(19). 3897-3904 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takei, I., Suzuki, K., Enta, Y., Dohki, K., Suzuki, T., Mizobe, Y., Hidai, M.: "Synthesis of a New Family of Heterobimetallic Tetranuclear Sulfido Clusters with Mo_2Ni_2S_x(x=4 or 5)or Mo_3M^1S_4(M^1=Ru, Ni, Pd) Cores"Organometallics. 22(9). 1790-1792 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takei, I., Wakebe, Y., Suzuki, K., Enta, Y., Suzuki, T., Mizobe, Y., Hidai, M.: "Synthesis of Cubane-Type Mo_3NiS_4 Clusters and Their Catalytic Activity for the Cyclizaition of Alkynoic Acids to Enol Lactones"Organometallics. 22(23). 4639-4641 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M., Nishibayashi, Y.: "Heterolytic Cleavage of Dihydrogen by Ruthenium and Molybdeniun Complexes"Recent Advances in Hydride Chemistty, Elsevier Science B.V. : Amsterdam. 117-138 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M., Mozobe, Y.: "Chemical Dinitrogen Fixation by Molybdenum and Tungsten Complexes.Insights from Coordination Chemistry"Molybdenum and Tungsten.Their Roles in Biological Processes(Metal Ions in Biological Systems), Marcel Dekker, Inc. : New York. Vol39. 121-161 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M., Mozobe, Y.: "Ammorna Synthesis by Transition Metal Complexes"Encyclopedia of catalysis, John Wiley & Sons, Inc : New York. 293-300 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M., Ishii, Y., Kuwata, S.: "Novel Chemical Transfonnations at Diruthenium Centers Bridged by Thiolato Ligands"Modem Coordination Chemistry : The Legacy of Joseph Chatt, The Royal Society of Cheistry : Cambridge, UK. 208-216 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hidai, M.: "Synthesis and Reactivities of Multinuclear Sulfur-Bridged Metal Complexes Ranging from Dinuclear to Hexanuclear Cores"Perspectives in Organometallic Chemnisimy, The Royal Society of Chemistry : Cambridge, UK. 62-73 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] I.Takei, K.Suzuki, Y.Enta, K.Dohki, T.Suzuki, Y.Mizobe, M.Hidai: "Synthesis of a New Family of Heterobimetallic Tetranuclear Sulfido Clusters with Mo_2Ni_2S_x (x=4 or 5) or Mo_3M'S_4 (M'=Ru, Ni, Pd) Cores"Organometallics. 22・9. 1790-1792 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] I.Takei, Y.Wakebe, K.Suzuki, Y.Enta, T.Suzuki, Y.Mizobe, M.Hidai: "Synthesis of Cubane-Type Mo_3NiS_4 Clusters and Their Catalytic Activity for the Cyclization of Alkynoic Acids to Enol Lactones"Organometallics. 22・23. 4639-4641 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Takemoto, S., Kawamura, H., Yamada, Y., Okada, T., Ono, A., Yoshikawa, E., Mizobe, Y., Hidai, M.: "Ruthenium Complexes Containing Bis(diarylamido)/Thioether Ligands : Synthesis and Their Catalysis for the Hydrogenation of Benzonitrile"Organometallics. 21・19. 3897-3904 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takagi, F., Seino, H., Mizobe, Y., Hidai, M.: "Synthesis of a New Tetrakis(hydrosulfido) Diiridium Complex and Its Conversion into Homo-and Heterometallic Sulfido-Hydrosulfido Clusters"Organometallics. 21・4. 694-699 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kuwata, S., Hashizume, K., Mizobe, Y., Hidai M.: "Structures and Reactivities of Palladium-Ruthenium Mixed-Metal Sulfido Clusters Derived from Disulfido-or Hydrosulfido-Bridged Diruthenium Complexes"Organometallics. 21・24. 5401-5407 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kuwata, S., Nagano, T., Matsubayashi, A., Ishii, Y., Hidai, M.: "Sulfur-Bridged Early-Late Heterobimetallics Synthesized by Incorporation of Titanium, Vanadium, and Molybdenum into Bis(hydrosulfido) Templates of Group 9 Metals"Inorganic Chemistry. 41・17. 4324-4330 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takagi, F., Seino, H., Hidai, M., Mizobe, Y.: "Preparation of a Heterobimetallic Cluster with Bridging Sulfido and Thiolato Ligands [{(η^5-C_5Me_5)Ru}{(η^5-C_5Me_5)Ir}_2(μ_3-S)(μ_2-SCH_2CH_2CN)_2Cl] and Its Transformations into Alkyne, CO, Isocyanide, and Iminoacyl Clusters"Organometallics. 22・5. 1065-1071 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Matsukawa, S., Kuwata, S., Ishii, Y., Hidai, M.: "Coordination behaviour of (diaryl disulfide)-bridged dinuclear thiairidaindan cores : ligand substitution by isocyanides, CO, hydrazines and hydroxylamine, and related reactions"Dalton Transactions. -・13. 2737-2746 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hidai, M., Mizobe, Y.: "Chemical Nitrogen Fixation by Using Molybdenum and Tungsten Complexes"Pure Appl.Chem.. 73. 261-263 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Kuwata, S., Kabashima, S., Ishii, Y., Hidai, M.: "A Ti_2Ru_2Pd_2 Oxo-Sulfido Cluster Synthesized by Linking Tow Rationally Preorganized TiRuPdS_2 Heterotrimetallic Units with an Oxo Ligand: Its Reaction with an Alkyne"J.Am.Chem.Soc.. 123. 3826-3827 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Takagi, F., Seino, H., Mizobe, Y., Hidai, M.: "Addition of Bridging-Hydrosulfido Ligands in Diiridium Complex to Acrylonitrile. Synthesis of Diiridium cyanoethylthiolato Complexes and RuIr_2 Sulfido-Cyanoethylthiolato Cluster"Can.J.Chem.. 79. 632-634 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Kuwata, S., Kabashima, S., Sugiyama, N., Ishii, Y., Hidai, M.: "Synthesis of TiRu_2 Heterobimetallic and TiRuM(M=Rh,Ir,Pd,Pt)Heterotrimetallic Sulfido Clusters from a Hydrosulfido-Bridged Titanium-Ruthenium Complex"Inorg.Chem.. 40. 2034-2040 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Ikeda, T., Mizobe, Y., Hidai, M.: "Incorporation of Three Phenylacetylene Molecules into an RhMo_2S_4 Trinuclear Sulfido Cluster Core,Forming Bridging Metallathiacyclobutene and Dithiolene Moieties"Organometallics. 20. 4441-4444 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Takemoto, S., Otsuka, K., Otsuka, T., Seino, H., Mizobe, Y., Hidai, M.: "Synthesis and Structures of p-tert-Butyltetrathiacalix[4]arene-dihydrides of Mo(IV) and W(IV)"Chem.Lett.. 6-7 (2002)

    • Related Report
      2001 Annual Research Report

URL: 

Published: 2001-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi