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Synthesis and Applications of Ultrafine Particles Derived From Organometallic Complexes

Research Project

Project/Area Number 09555245
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 触媒・化学プロセス
Research InstitutionTokyo University of Agriculture & Technology

Principal Investigator

KOMIYA Sanshiro  Tokyo University of Agriculture and Technology, Department of Applied Chemistry, Professor, 工学部, 教授 (00111667)

Co-Investigator(Kenkyū-buntansha) KOMINE Nobuyuki  Tokyo University of Agriculture and Technology, Department of Applied Chemistry, Research Associate, 工学部, 助手 (90302918)
HIRANO Masafumi  Tokyo University of Agriculture and Technology, Department of Applied Chemistry, Associate Professor, 工学部, 講師 (70251585)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 1999: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1998: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1997: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordsultrafine particles / platinum / palladium / siloxo ligand / hydrogenolysis / catalyst / 有機金属錯体 / 担持触媒 / 白金シロキソ錯体
Research Abstract

Group 10 metal complexes with a siloxo ligand, M(Me)(OSiPhィイD23ィエD2)(cod) [1:M = Pt, 2 : M = Pd, cod = 1,5-cyclooctadiene] are newly prepared by the metathetical reaction of M(Me)(Cl)(cod) with NaOSiPhィイD23ィエD2. These complexes are found to form nano-scale ultrafine Pt or Pd particles with concomitant formation of cyclooctane, methane and triphenylsilanol by exposure to molecular hydrogen (1 atm) under ambient conditions. Adsorption of complex 1 on the surface of silica followed by exposure to HィイD22ィエD2 results in the formation of ultrafine Pt particles on silica (mean diameter = 8.2 ± 6.2 nm). These silica-supported Pt particles act as catalyst for hydrogenation of olefins and for reduction of nitrogen oxides. On the other hand, hydrogenolysis of polymer films containing 1 also gives polymer containing highly dispersed Pt particles with mean diameters of 1-8 nm. The Pt metal particles size decreases with decrease of reduction temperature and concentration of 1 in the polymer. The polar polymer such as poly(methyl methacrylate) gives the smallest particles less than 1 nm diameters. These particles are characterized as pure Pt crystals by TEM, FE-TEM, and XPS analyses.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] S. Komiya et al.: "Synthesis of Hydridoplatinum-Molybdenum(or Tungsten) heterodinuclear Complexes by βHydrido Elimination of (dppe)EtPt-WCp(CO)_3. Selective Hydride Transfer from Pt to Mo"J. Mol. Catal. A. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Komiya et al.: "Regio- and Stereoselective Insertion Reactions of Thiiranes into Pt-Mn(or Re) Bond in Organoplatinum-manganese or -rhenium Heterodinuclear Complexes as Intermediate toward Desulfurization Reaction"J. Am, Chem, Soc.. 122. 170-171 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Nakahara et al.: "Synthesis and Structure of Thiolato Bridged Early-Late Heterobimetallic Complexes with Methyl Group"J. Organomet. Chem.. 572. 81-85 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Fukuoka et al.: "Synthesis of organo(siloxo)platinum and-palladium complexes and preparation of supported nanoclusters by facile ligand reduction"Inorg. Chim. Acta. 294. 266-274 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R. Domeki, et al.: "effect of Pt precursors on N_2/N_2O selectivity for selective reduction of NO by hydrocarbon on supported Pt catalysts"Chem. Lett.. 515-516 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Fukuoka, et al.: "Water-soluble rhodium and iridium complexes with tris(hydroxymethy)phosphine and their activity in biphasic hydroformylation and hydrogenation"J. Chem. Soc., Chem. Commun.. 489-490 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Komiya., et al.: "Synthesis of Hydridoplatium-Molybdenum (or Tungsten) Heterodinuclear Complexes by β-Hydrido Elimination of (dppe)EtPt-MoCp(CO)ィイD23ィエD2 Selective hydride Transfer from Pt to Mo"J. Mol. Catal. A.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Komiya., et al.: "Regio-and Stereoselective Insertion Reactions of Thiiranes into Pt-Mn (or Re) Bond in Organo-platinum-manganese or -rhenium Heterodinuclear Complexes as Intermediate toward Desulfurization Reaction"J. Am. Chem. Soc.. 122. 170-171 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Nakahara, et al.: "Synthesis and Structure of Thiolato Bridged Early-Late Heterobimetallic Complexes with Methy Group"J. Organomet. Chem.. 572. 81-85 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Fukuoka, et al.: "Synthesis of Organo(siloxo)platinum and -palladium Complexes and Preparation of Supported Nanoclusters by Facile Ligand Reduction"Inorg. Chim. Acta.. 294. 266-274 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Domeki, et al.: "Effect of Pt Precursors on NィイD22ィエD2/NィイD22ィエD2O Selectivity for Selective Reduction of NO by Hydrocarbon on Supported Pt Catalysts"Chem. Lett.. 515-516 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Fukuoka, et al.: "Water-soluble Rhodium and Iridium Complexes with Tris(hydroxymethyl)phosphine and Their Activity in Biphasic Hydroformylation and Hydrogenation"J. Chem. Soc., Chem. Commun.. 489-490 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.Komiya et al.: "Synthesis of Hydrideplatinum-Molybdenum (or Tungsten) Heterodinuclear Complexes by β Hydride Elimination of (dppe) EtPt-WCp(CO)_3. Selective Hydride Transfer from Pt to Mo (or W)"J. Mol. Catal. A. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Komiya et al.: "Regio- and Stereoselective Insertion Reactions of Thiiranes into Pt-Mn (or Re) Bond in Organoplatinum-manganese or -rhenium Heterodinuclear Complexes as Intermediate toward Desulfurization Reaction"J. Am. Chem. Soc.. 122. 170-171 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Nakahara et al.: "Synthesis and Structure of Thiolato Bridged Early-Late Heterobimetallic Complexes with Methyl Group"J. Organomet.Chem.. 572. 81-85 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Fukuoka et al.: "Synthesis of organo(siloxo)platinum and -palladium complexes and preparation of supported nanoclusters by facile ligand reduction"Inorg. Chim. Acta. 294. 266-274 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.Domeki, et al.: "Effect of Pt precursors on N _2/N_2O selectivity for selective reduction of NO by hydrocarbon on supported Pt catalysts"Chem. Lett.. 515-516 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Fukuoka, et al.: "Water-soluble rhodium and iridium complexes with tris(hydroxymethyl)phosphine and their activity in biphasic hydroformylation and hydrogenation"J. Chem. Soc., Chem. Commun.. 489-490 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Komiya et al.: "Hydrogen Transfer in Pt-Mo Heterodinuclear Hydride Complexes Promoted by Alkynes" Chem.Lett.29-30 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Komiya et al.: "Tail-to-tail Dimerization of Acrylonitrile Catalyzed by Low-Valent Ruthenium Complexes" Bull.Chem.Soc.Jpn.71. 1409-1415 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Komiya et al.: "Synthesis and Structure of Thiolato Bridged Pt-Ti Heterobimetallic Complexes with Methyl Group" J.Organomet.Chem.572. 81-85 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hiroaki Kubo: "Synthesis,Structure and Reactivity of(η_6-Naphthalene)iron(0)Complex Having a 1,2-Bis(dicyclohexylphosphino)ethane Ligand" J.Organomet.Chem.in press.

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Hirano: "Successivc O-C/O-H and sp^3C-H Bond Activation of ortho Substituents in Allyl Phenyl Ethers and Phenols by a Ruthenium(0)Complex" Organometallics. 17. 501-503 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Jose G.Planas: "C-S Bond Cleavage of Allyl Thioethers by Zerovalent Ru Complexes" Chem.Lett.123-124 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Toshiyuki Yasuda: "Hydrogen Transfer in Pt-Mo Heterodinuclear Hydride Complexes Promoted by Alkynes" Chem.Lett.29-30 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Yoko Usui: "Hydrogen Abstraction from Transition Metal Hydrides by Gold Alkoxides Giving Gold-Containing Heteodinuclear Complexes" Chem.Lett.981-982 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Hirano: "Synthesis and Reactions of Dinitrogen Complex of Iron(0),Fe(N_2) (depe)_2" J.Chem.Soc.,Dalton Trans. 3453-3458 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Hirano: "Activation of Coordinatcd Carbon Dioxidc in Fe(CO_2)(depe)_2 by Group 14 Electrophiles" Organometallics. 16. 4206-4213 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Atsushi Fukuoka: "Insertion of CO into a CH_3-pdBond in a Heterodinuclear Complex (dpe)Mepd‐Co(CO)_4" Chem.Lett.377-378 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Atsushi Fukuoka: "Enbancement of β‐Hydrogen Elimination Reaction on Platinum‐containing HererOdinuclcar Complexes" Chem.Lett.329-330 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Hirano: "Unexpected Ligand Displacement of Ru(cod)(cot)with Trimethylphospline to Give fac‐Ru(6‐η^1:1‐3‐η^3‐C_8H_<10>)(PMe_3)_3" Chem.Lett.297-298 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Sanshiro Komiya: "Synthesis of Organometallic Compounds" Wiley, 433 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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