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SYNTHESIS OF DIIRON COMPLEXES AS EFFICIENT CATALYSTS FOR OXIDATIVE ALKANE-HYDROXYLATION

Research Project

Project/Area Number 06804040
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物質変換
Research InstitutionDOSHISHA UNIVERSITY,FACULTY OF ENGINEERING

Principal Investigator

KODERA Masahito  DOSHISHA UNIVERSITY,FACULTY OF ENGINEERING,DEPARTMENT OF MOLECULAR SCIENCE AND TECHNOLOGY,ASSOCIATE PROFESSOR, 工学部, 助教授 (00183806)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1994: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsHexapyridine ligand / Diiron complex / Alkane-hydroxylation / Methane monooxygenase / Calboxylate ligand / Diiron dioxygen complex / Hydrogen peroxide / メタンモノオキシナーゼ / カルボキシル基の効果 / ヘキサピリジン配位子の合成 / μ-オキソ架橋二核鉄錯体 / アルカンの水酸化 / 触媒反応 / メタンモノオキシゲナーゼモデル / 錯体触媒 / 単結晶X線構造解析
Research Abstract

2,2'-Bis [di (2-pyridyl) methyl] -6,6'-ethylenedipyridine (L^1) and 3,3-di-2-pyridylpropanoic acid (L^2) have been synthesized. These ligands form spontaneously mu-oxo-di-m-acetatodiiron (III) complexes, [Fe_2 (O) (OAc) _2 (L^1)] (X) _2 (x=ClO_4 1a and CF_3SO_3 1b) and [Fe_2 (O) (OAc) _2 (L^2) _2] (2), by the reaction with iron (III) ion and sodium acetate.
These diiron complexes funciton as a model of soluble methane monooxygenase (sMMO) which catalyzes the hydroxylation of methane to methanol in methanotroph. When m-chloroperbenzoic acid (m-CPBA) is used as oxidant, 1 catalyzes the oxygenation of cyclohexane, methylcyclohexane, adamantane, n-alkanes, and ethylbenzene. The catalytic turnover number and the turnover frequency for the oxygenaiton of cyclohexane with 1 are larger than 1000 and 100 cycles/min, respectively. The turnover number of 1 is ten-fold larger than that of a cyclohexane/ (tetraphenyl-porphynato) iron (III) /m-CPBA system. The compound 2 catalyzes the same reaction. … More The reaction ctatlyzed by 2 is much faster than that of 1. The coordination of carboxylate ion makes 2 electrically neutral and enhances the solubility of 2 in non-polar solvent, leading to the rapid and efficient alkane functionalization.
A pale brown solution of 1b in CH_3CN/cyclohexane turns purple by the addition of H_2O_2. The electronic absorption spectrum of the purple solution shows two bands at ca. 500 (epsilon : 1000) and 600 (epsilon : 1000 M^<-1>cm^<-1>) nm, suggesting the formation of a peroxodiiron (III) complex [Fe_2 (O) (OAc) (O_2) (L^1)] (CF_3SO_3) (3). A half life time of 3 in CH_3CN/cyclohexane is 79 min, showing that 3 is thermally quite stable. In order to isolate 3, the purple solution is concentrated to dryness. FAB Mass spectrum of the isolated 3 shows relatively strong parent peaks at m/z : 739,707, and 679, which are assignable to [Fe_2 (O) (OAc) (O_2) (L^1)] ^+, [Fe _2 (O) (OAc) (L^1)] ^+, and [Fe_2 (O) (O_2) (L^1)] ^+, respectively. These data reasonably explain the formation of the peroxodiiron (III) complex 3. Less

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (8 results)

All Other

All Publications (8 results)

  • [Publications] 大川尚士: "Dithiooxalato(dto)-Bridged Binuclear Assemblies(NPr_4[MCr(dto)_3])_x(M=Co, Ni, Zn, Fe,・NPr_4=Tetrapropy(ammonium Ion): New Complex-Based" Bull. Chem. Soc. Jpn.67. 2139-2144 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 大塚信一郎: "Dinuclear Cu^<II>M^<II>(M=Co, Ni, Cu, or Zn) and Cu^<II>Cu^I Complexes of a Phenol-based Dinucleating Macrocycle with Dissimclar N_2O_2 and N_2O_2S Sites" J. Chem. Soc. Dalton Trans.2599-2604 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 小寺政人: "Nonheme Monooxygenase" Oxygenases and Model Systems. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Okawa, M.Mitsumi, M.Ohba, M.Kodera, and N.Matsumoto: "Dithiooxalate (dto) -Bridged Bimetallic Assemblies {NPr_4 [MCr (dto) _3]} _x (M=Fe, Co, Ni, Zn ; NPr_4=Terapropylammonium Ion) : New Complex-Based Ferromagnets" Bull.Chem.Soc.Jpn.Vol.67, No.8. 2139-2144 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] S.Ohtsuka, K.Motoda, M.Ohba, M.Kodera, and H.Okawa: "Dinuclear Cu^<II>M^<II> (M=Co, Ni, Cu, or Zn) and Cu^<II>Cu^I Complexes of a Phenol-based Dinucleating Macrocycle with Dissimilar N_2O_2 and N_2O_2S Sites" J.Chem.Soc.Dalton Trans.No.16. 2599-2604 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Kodera, K.Kano, and T.Funabiki: Nonheme Monooxygenases. Oxygenases and Model Systems, T.Funabiki (Ed), Kluwer Academic Publishers, (in press),

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 大塚信一郎: "Dinuclear Cu^<II>M^<II>(M=Co, NiCu or Zn)and Cu^<II>Cu^I Complexed of a Plsnol based Dimdeating Macrocyck with DissimilarNiO_2 and N_2O_2S Sites"" J. Chem. Soc. Dalton Trans.2599-2604 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 小寺,政人: "Nonheme Monooxyglnases" Oxygenases and Model Systems. (in press).

    • Related Report
      1995 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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