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Development of Catalysts for Epoxidation of Olefins

Research Project

Project/Area Number 61850154
Research Category

Grant-in-Aid for Developmental Scientific Research

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

MATSUDA Yoshihisa  Kyushu University, 工学部, 助教授 (10037757)

Co-Investigator(Kenkyū-buntansha) 盛満 耕造  出光興産, 中研, 研究主任
熊沢 尚  出光興産, 中研, 研究主任
HISAEDA Yoshio  Kyushu University, 工学部, 助教授 (70150498)
MORIMITSU Kozo  Idemitsu Kosan
KUMASAWA Takashi  Idemitsu Kosan
Project Period (FY) 1986 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥6,700,000 (Direct Cost: ¥6,700,000)
Fiscal Year 1988: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1986: ¥3,800,000 (Direct Cost: ¥3,800,000)
KeywordsEarly transition metals / Porphyrin complexes / Photoredox chemistry / Epoxidation / エポキシ化反応 / 時間分解ESR / 軸配位子の反応 / 三重項ラジカル対 / モリブデンポルフィリン錯体 / 光酸素化反応 / 分子酸素の活性化
Research Abstract

Niobium(V) and molybdenum(V) porphyrins were prepared. Molybdenum complexes had an octahedral structure with an oxo and an alkoxo ligand on their axial site, while tri-u-oxo dimer of niobium(V) porphyrins had cis-hepta-coordinated one. Complexes catalyzed photochemical epoxidation of olefins in benzene upon aerobic irradiation of with visible light. Photochemical reactions of above complexes were followed by means of visible absorption and ESR spectroscopy.
Nionium(V) and molybdenum(V) porphyrins were reduced in benzene upon anaerobic irradiation with visible light affording corresponding pentacoordinate complexes. Homolysis of an axial coordination bond took place during the photoreduction and axial ligands were released as corresponding radical species. The reduced complexes were oxidized in benzene by molecular oxygen upon aeration resuting superoxide complexes. The superoxide complexes transferred an oxygen atom to an olefin added in the soultion to form corresponding epoxide.
The photoreduction of the complexes was revealed by means of time-resolved ESR spectroscopy. The photoreduction, the homolysis of the axial coordination bond, proceeded via a charge transfer triplet state and a triplet pair of a radical and a reduced central metal. The superoxide complex was formed by reaction of molecular oxygen with the triplet pair. Addition of molecules which could coordinate at the axial site of the complexes disturbed the formation of the superoxide complexes.
No cis-trans isomerization took place in the photo-epoxidation process suggesting an ionic nature of the intermediate. Olefins having a terminal double bond showed lower activity than ones having an internal duble bond. Olefins with more alkyl substituent groups had higher activity than those with less substituent groups. Introduction of picket fence type substituents into the porphyrin ligand improved both activity and selectivity.

Report

(3 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] Yoshihisa Matsuda: Bull.Chem.Soc.Jpn.59. 1839-1844 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa Matsuda: Chem.Lett.1988. 625-628 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa,Matsuda: "Transition-Metal Complexes of Pyrrole Pigments. XXII. Photoredox Behavior of Oxo(tetra-p-tolylporphinato)molybdenum(V)" Bull. Chem. Soc. Jpn.59. 1839-1844 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa,Matsuda: "Photochemical Epoxidation of Olefins with Molecular Oxygen Activated by Oxo(tetra-p-tolylporphinato)molybdenum(V)" Chem. Lett.1988. 625-628 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yohihisa,Matsuda: "Photochemistry of Niobium Porphyrins in the Presence of Phenols" Chem. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa,Matsuda: "Photo-catalytic Epoxidation of Olefins with Molecular Oxygen in the Presence of Molybdenum Porphyrins" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa,Matsuda: "Photoreduction of Niobium Porphyrins Revealed by Means of Time-resolved ESR Spectroscopy" Cheam. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Yoshihisa Matsuda: Chem.Lett.1988. 625-628 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Yoshihisa Matsuda: Bull.Chem.Soc.Jpn.59. 1839-1844 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] Yoshihisa Matsuda: Chemistry Letters.

    • Related Report
      1986 Annual Research Report
  • [Publications] Yoshihisa Matsuda: Chemistry Letters.

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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