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MECHANISM OF OXYGEN ACTIVATION BY IRON-CHLORIN COMPLEXES AND THEIR REACTIVITIES.

Research Project

Project/Area Number 05453043
Research Category

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

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionOKAZAKI NATIONAL RESEARCH INSTITUTES (1994)
Kyoto University (1993)

Principal Investigator

WATANABE Yoshihito  OKAZAKI NATIONAL RESEARCH INSTITUTES,INSTITUTE FOR MOLECULAR SCIENCE,PROFESSOR, 分子科学研究所, 教授 (10201245)

Co-Investigator(Kenkyū-buntansha) MORISHIMA Isao  GRADUATE SCHOOL OF ENGINEERING,KYOTO UNIVERSITY,PROFESSOR, 工学部, 教授 (50026093)
Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1994: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1993: ¥4,400,000 (Direct Cost: ¥4,400,000)
Keywordschlorin / compound I / cation radical / cytochrome d / heme / Compound I / cytochrome d / 鉄クロリン錯体 / 酵素モデル / 酸素活性化 / 反応機構
Research Abstract

Preparation and characterization of reaction intermediates observed or proposed in the catalytic cycle chlorin-containing heme enzymes. Catalases in Escherichia coli and Neurospora crassa possess iron chlorin prosthetic groups and catalyze dismutation of hydrogen peroxide. While a high-valent iron chlorin complex (chlorin compound I) is postulated to be a reaction intermediate in the catalytic cycle of these catalases, the high-valent chlorins have not been prepared and thus the details of chlorin compound I are still obscure. Thus, we have prepared the chlorin compound I by employing a sterically hindered chlorin model complex. The oxo-iron (IV) chlorin pi-cation radical has been successfully prepared.
Models of oxo-iron (IV) chlorin complexes have been prepared and characterized in detail to elucidate the unusual properties of the intermediate of cytochrome d. The six-coordinated oxo-ferrylchorin complex exhibited an unusual splitting of the hyperfine-shifted pyrroline proton resonances in its NMR spectrum, suggestive of deformation of the pyrroline ring of the chlorin complex.
The model complexes of the putative reaction intermediate, peroxo-Fe (III), have been synthesized. The peroxo complexes have electronics structures similar to those of the corresponding porphyrin complexes. However, unusual features have been observed in their deuterium NMR spectra, rationalized by large deformation of the pyrroline ring of the peroxo complexes.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] Tsurumaki,H.: "Preparation,Characterization,and Reactions of Novel Iron (III) Porphyrin Dication Complexes." J.Am.Chem.Soc.115. 11784-11788 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa,S.: "Preparation and Characterization of Oxoiron (IV) Chlorin Complexes as the First Models for a Reaction Intermediate in the Catalytic Cycle of Cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa,S.: "Spectroscopic Characterization of Peroxo-Iron (III) Chlorin Complexes. The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa,S.: "NMR Studies of π-Cation Radical Complexes of Iron (III) and Oxoiron (IV) Chlorins. Models for Reaction Intermediates of Chlorin-Containing Heme Enzymes." J.Am.Chem.Soc.116. 5832-5838 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Mizutani,Y.: "Resonace Raman Characterization of Iron (III) Porphyrin N-Oxide : Evidence for an Fe-O-N Bridged Structure." J.Am.Chem.Soc.116. 3439-3441 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Machii,K.: "Acylperoxo-Iron (III) Porphyrin Complexes : A New Entry of Potent Oxidants for the Alkene Epoxidation." J.Am.Chem.Soc.117. 6691-6697 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Yamaguchi, K.; Watanabe, Y.; Morishima, I.: "Direct Observation of the Push Effect on the O-O Bond Cleavage of Acylperoxoiron (III) Porphyrin Complexes" J.Am.Chem.Soc.115. 4058-4065 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Tsurumaki, H.; Watanabe, Y.; Morishima, I.: "Preparation, Characterization, and Reactions of Novel Iron (III) Porphyrin Dication Complexes." J.Am.Chem.Soc.115. 11784-11788 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Tokita, Y.; Yamaguchi, K.; Watanabe, Y.; Morishima, I.: "Preparation, Characterization, and Reaction of Novel Dioxoruthenium (VI) Porphyrin Cation Radical Complexes." Inorg.Chem.32. 329-333 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Tsurumaki, H.; Watanabe, Y.; Morishima, I.: "Three Isoelectronic Structures of One Electron Oxidized Nickel Porphyrins" Inorg.Chem.33. 4186-4188 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Watanabe, Y.; Nakashima, S.; Kitagawa, T.; Morishima, I.: "Preparation and Characterization of Oxoiron (IV) Cholorin Complexes as the First Models for a Reaction Intermediate in the Catalytic Cycle of Cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Watanabe, Y.; Morishima, I.: "Spectroscopic Characterization of Peroxo-Iron (III) Chlorin Complexes. The First Model for a Reaction Intermediate of Cytochrome d." Inorg.Chem.33. 306-313 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Watanabe, Y.; Morishima, I.: "NMR Studies of pi-Cation Radical Complexes of Iron (III) and Oxoiron (IV) Chlorins. Models for Reaction Intermediates of Chlorin-Containing Heme Enzymes." J.Am.Chem.Soc.116. 5832-5838 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Watanabe, Y.; Morishima, I.: "The First Observation of Dynamic Ruffling Inversion of an Iron (III) Dihydroxychlorin Complex by Proton NMR Spectroscopy." Tetrahedron Letters. 35. 4141-4144 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Sakamoto, E.; Watanabe, Y.; Morishima, I.: "Formation of Nitrosyl-Iron (II) beta-Oxoporphyrin pi-Cation Radical Complexes. Models for a Reaction Intermediate of Dissimilatory Nitrite Reductases." J.Chem.Soc., Chem.Commun. 935-936 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Mizutani, Y.; Watanabe, Y.; Kitagawa, T.: "Resonace Raman Characterization of Iron (III) Porphyrin N-Oxide : Evidence for an Fe-O-N Bridged Structure." J.Am.Chem.Soc.116. 3439-3441 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Nagano, S.; Tanaka, M.; Watanabe, Y.; Morishima, I.: "Putative Hydrogen Bond Network in the Heme Distal Site of Horseradish Peroxidase." Biochem.Biophys.Res.Commun.207. 417-423 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Machii, K.; Watanabe, Y.; Morishima, I.: "Acylperoxo-Iron (III) Porphyrin Complexes : A New Entry of Potent Oxidants for the Alkene Epoxidation." J.Am.Chem.Soc.117. 6691-6697 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Ozawa, S.; Sakamoto, E.; Ichikawa, T.; watanabe, Y.; Morishima, I.: "Model Studies of Nitrosyl Intermediates in the Catalytic Cycle of Dissimilatory Nitrite Reductases." Inorg.Chem.34 (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] S.Ozawa: "Spectroscopic Characterization of Peroxo-Iron(III) Chlorin Complexes.The First Model for a Reaction Intermediate of Cytochrome d Terminal Oxidase." Inorg.Chem.33. 306-313 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Ozawa: "Preparation and Characterization of Oxoiron(IV) Chlorin Complexes as the First Models for a Reaction Intermediate in the Catalytic Cycle of Cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Ozawa: "NMR Studies of p-Cation Radical Complexes of Iron(III) and Oxoiron(IV) Chlorins.Models for Reaction Intermediates of Chlorin-Containing Heme Enzymes." J.Am.Chem.Soc.116. 5832-5836 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Ozawa: "Formation of Nitrosyl-Iron(II) b-Oxoporphyrin p-Cation Radical Complexes.Models for a Reaction Intermediate of Dissimilatory Nitrite Reductases." J.Chem.Soc.Chem.Commun.935-936 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Mizutani: "Resonace Raman Characterization of Iron(III) Porphyrin N-Oxide:Evidence for an Fe-O-N Bndoed Structure." J.Am.Chem.Soc.116. 3439-3441 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Ozawa: "The First Observation of Dynamic Ruffling Inversion of an Iron(III) Dihydroxychlorin Complex by Proton NMR Spectroscopy." “Tetrahedron Lett.35. 4141-4144 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Shinji Ozawa: "Spectroscopic characterization of peroxo-iron(III) chlorin complexes.The first model for a reaction intermediate of cytochrome d." Inorg.Chem.33. 306-313 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Shinji Ozawa: "Preparation and characterization of oxoiron(IV) chlorin complexes as the first models for a reaction intermediate in the catalytic cycle of cytochrome d." J.Am.Chem.Soc.116. 634-641 (1994)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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