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Liquid-phase Dehydrogenation Catalysis for Alkane with Metal Cluster Complexes

Research Project

Project/Area Number 04453077
Research Category

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

Allocation TypeSingle-year Grants
Research Field 工業物理化学・複合材料
Research InstitutionThe University of Tokyo

Principal Investigator

SAITO Yasukazu  The Univ.Tokyo, Faculty of Engineering, Professor, 工学部, 教授 (10010761)

Co-Investigator(Kenkyū-buntansha) YAMASHITA Masaru  The Univ.Tokyo, Research Associate, 工学部, 助手 (30239983)
ITAGAKI Hiroaki  The Univ.Tokyo, Research Associate, 工学部, 助手 (00203076)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 1993: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1992: ¥6,700,000 (Direct Cost: ¥6,700,000)
KeywordsAlkane Dehydrogenation Catalyst / Ruthenium Cluster Complex / Platinum Cluster Complex / Catalyst Surface Modification with Cluster Complex / Carbonyl Ligand Dissociation / Diphosphine-bridged Complex / Rhodium Dinuclear Complex / Iridium Dinuclear Complex / ルテニウム3核クラスター / 白金15核クラスター / シロクオクタン / エチルシクロヘキサン / 還流加熱条件 / シクロオクテン / エチルベンゼン
Research Abstract

A ruthenium carbonyl cluster complex Ru_3(CO)_<12> exhibited homogeneous catalysis for cyclooctane dehydrogenation, yielding cyclooctene and dihydrogen at T.O.N.= 69, whereas cyclohexanes were unreactive even under boiling and refluxing conditions in contrast to catalytically-active platinum or platinum-ruthenium composite fine particles.
Pt-Ru composite catalysts were prepared from an ionic pair of Cs_2[Pt_3(CO)_6]_5 and [Ru(C_6Me_6)_2](BF_4)_2 by precepitation on a carbon support, followed by a heat treatment or from the surface modification of a platinum catalyst with a ruthenium hydrido-carbonyl complex H_4Ru_4(CO)_<12>. These composite catalysts were highly-active for dehydrogeno-aromatization of ethylcyclohexane.
Photocatalytic alkane dehydrogenation was demonstrated with the A-frame dinuclear complexed of rhodium and iridium. It is noteworthy that the photoactive band at 365 nm of RhCl(CO)(PR_3)_2 is now extended to 475 nm (dinuclear Rh) and to 520 nm (dinuclear Ir), since it is important from the viewpoint of solar energy utilization.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] T.Fujii,et al.: "Thermocatalytic Dehydrogenation of Alkanes with Wilkinson Complexes" J.Chem.Soc.,Dalton Trans.517-520 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki,et al.: "Photocatalysis of Cyclooctane Dehydrogenation by the A-frame Dinuclear Rhodium Complex[Rh_2(μ-S)(CO)_2(dppm)2]" J.Chem.Soc.,Dalton Trans.1689-1693 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki,et al.: "Catalytic Cyclooctane Photodehydrogenation at Unusually Low Photon Energy with a Dinuclear Iridium Complex" Chem.Lett.2097-2098 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki,et al.: "Photocatalysis of RhCl(PCy_3)_2 for Cyclohexane Dehydrogenation:Thermal Dissociation of C-H Bond and Photoelimination of H_2" Bull.Chem.Soc.Jpn.67(in press). (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Yukawa,et al.: "Dehydrogeno-aromatization of Cyclohexanes with Suspended Noble-metal Catalysts" J.Chem.Soc.,Faraday Trans.89. 3641-3644 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 斉藤泰和: "液相脱水素触媒" 触媒. 35. 190-192 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Yamashita,N.Mou,Y.Saito,et al.: "New Energy Systems and Conversions" Universal Academy Press,Inc., 4 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] 斉藤泰和: "季刊化学総説 光が関わる触媒化学" 学会出版センター, 10 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Fujii, Y.Higashino, Y.Saito: "Thermocatalytic Dehydrogenation of Alkanes with Wilkinson Complexes" J.Chem.Soc., Dalton Trans.517-520 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki, H.Einaga, Y.Saito: "Photocatalysis of Cyclooctane Dehydrogenation by the A-Frame Dinuclear Rhodium Complex [Rh_2(mu-S)(CO)_2(dppm)_2]" J.Chem.Soc., Dalton Trans.1689-1693 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki, H.Einaga, Y.Saito: "Catalytic Cyclooctane Photodehydrogenation at Unusually Low Photon Energy with a Dinuclear Iridium Complex" Chem.Lett.2097-2098 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Itagaki, H.Murayama, Y.Saito: "Photocatalysis of RhCl(PCy_3)_2 for Cyclohexane Dehydrogenation : Thermal Dissociation of C-H Bond and Photoelimination of H_2" Bull.Chem.Soc.Jpn.67(in press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] K.Yukawa, X.Li, T.Fujii, et al.: "Dehydrogeno-aromatization of Cyclohexanes with Suspended Noble-metal Catalysts" J.Chem.Soc., Faraday Trans.89. 3641-3644 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Saito: "Liquid-phase Dehydrogenation Catalyst" Shokubai (Catalyst). 35. 190-192 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Yamashita, N.Mou, Y.Sato, et al.: "New Energy Systems and Conversions" Universal Academy Press, Inc.4 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Y.Saito: "Quartery Chemistry Review -Catalytic Chemistry Associated with Photon-" Gakkai Shuppan Center, 10. 10 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Fujii,Y.Higashino,Y.Saito: "Thermocatalytic Dehydrogenation of Alkanes with Wilkinson Complexes" J.Chem.Soc.,Dalton Trans.517-520 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Itagaki,H.Einaga,Y.Saito: "Photocatalysis of Cyclooctane Dehydrogenation by the A-frame Dinuclear Rhodium Complex [Rh_2(μ-S)(CO)_2(dppm)_2]" J.Chem.Soc.,Dalton Trans.1689-1693 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Itagaki,H.Einaga,Y.Saito: "Catalytic Cyclooctane Photodehydrogenation at Unusually Low Photon Energy with a Dinuclear Iridium Complex" Chem.Lett.2097-2098 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Itagaki,H.Murayama,Y.Saito: "Photocatalysis of RhC1(PCy_3)_2 for Cyclohexane Dehydrogenation:Thermal Dissociation of C-H Bond and Photoelimination of H_2" Bull.Chem.Soc.Jpn.67(in press). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Yukawa,X.Li,T.Fujii,et al: "Dehydrogeno-aromatization of Cyclohexanes with Suspended Noble-metal Catalysts" J.Chem.Soc.,Faraday Trans.89. 3641-3644 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 斉藤 泰和: "液相脱水素触媒" 触媒. 35. 190-192 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Yamashita,N.Mou,Y.Saito,et al.: "New Energy Systems and Conversions" Universal Academy Press,Inc., 4 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] 斉藤 泰和: "季刊化学総説 光が関わる触媒化学" 学会出版センター(印刷中), (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Yukawa,H.Kanaboshi,Y.Saito: "Thermocatalytic Dehydrogenation of Cyclooctane with Heterogenized Trinuclear Ruthenium Cluster Complex" Chem.Lett.NO.7. 1177-1180 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Hama,X.Li,K.Yukawa,Y.Saito: "Thermal Dehydrogenation of Cycloalkanes by Supported Platinum Catalysts" Chem.Lett.NO.12. 2463-2466 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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