• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of multicompont systems of metal complexes/molecular oxygen/electron Transfer that function oxygenale-like catalytic activity

Research Project

Project/Area Number 09555270
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 工業物理化学
Research InstitutionKyoto University

Principal Investigator

FUNABIKI Takuzo  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (70026061)

Co-Investigator(Kenkyū-buntansha) SUGIURA Yukio  Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (40025698)
TAKANO Mikio  Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (70068138)
TANAKA Tsunehiro  Kyoto University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (70201621)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥12,300,000 (Direct Cost: ¥12,300,000)
Fiscal Year 1999: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1997: ¥6,700,000 (Direct Cost: ¥6,700,000)
KeywordsNonheme Iron Complex / Oxygenases / Monooxygenases / Dioxygenases / Electron Transfer / Oxygenative Cleavages of Aromatics / Nonheme Manganese Complex / Enxyme Model Catalysis / 非ヘムマンガン錯体 / クロロカテコール / 酵素機能発現
Research Abstract

In the project for development of new monooxygnase- and dioxygenase-like catalytic reactions in the multicomponent system of nonheme iron complexes/molecular oxyen/electron transfer, we were successful to develop new reactions in the oxygenation of aromatics, alkanes, and alkenes catalyzed by Fe(III), Fe(II) and Mn(II) complexes. In the monooxygenase functional model systems, we have developed a new system using catecholateiron(III) comlex as the iron center and hydroquinones as the electron and proton donors. This gave characteristic results in the monooxygenation of alkanes, alkenes, and aromatics. In the functional model reactions for α-keto acid-dependent dioxygenases, new oxygenations were developed in the selective epoxidation of alkenes such as cyclooctene and norbornene, hydroxylation or carbonylation of alkanes such as adamantane and cyclohexane. Selective oxygenations of catechols by iron(III) complexes has been extensively studied. Besides the selective intradiol oxygenation by Fe(III), we have developed a new reaction by Mn(II) complex. This is the first model system for the manganese-dependent catechol dioxygenases. As an intermediate, we have isolated a Mn(II)-semiquinonate complex as a new type of complex. The structure of the complex was clarified by X-ray crystallographif analysis, ESI-Mass, ESR, IR, UV-VIS spectra. What is the most interesting is that the complex maitains the electronic structure of Mn(II)-semiquinonate configuration. This is a very important information for the mechanism of catechol dioxygenases.

Report

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

    (29 results)

All Other

All Publications (29 results)

  • [Publications] Ryo Yamahara: "(Catecholato) iron (III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-baound intermediate of intradiol-cleaving catechol deoxygenates"Inorg. Chim. Acta,. 300-302. 587-596 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Mechanism of Oxygenative Cleavage of Catechols by Nonheme Iron Complexes in Relevance to Catechol Dioxygenases Studied by Quantum Chemical calculations"J. Mol. Cat. A.. 150. 37-47 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato (pyridine) iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases"Inorg. Chim. Acta,. 275-276. 222-229 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron (III) complexes and its relevance to chlorocatechol dioxygenases"Angew Chem. Inern. Ed. Eng.. 37. 513-515 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "ortho-Hydroxylation of 4-tert-Butylphenol by Nonheme Iron (III) Complexes as a Functional Model Reactio for Tyrosine Hyerokylase"J. Chem. Soc., Chem.Commun. 151-152 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenases and Model Systems"Kluwer Academic Publishers. 393 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] R. Yamahara, S. Ogo, Y. Watanabe, T. Funabiki, K. Jitsukawa, H. Masuda, H. einaga: "(Catecholato) iron (III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-baound intermediate of intradiol-cleaving catechol dioxygenases"Inorg.Chim.Acta. 300-302. 587-596 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Funabiki, t. Yamazaki: "Mechanism of oxygenative cleavage of catechols by nonheme iron complexes in relevance to catechol dioxygenases studied by quantum chemical calculations"J.Mol.Cat.A.Chemical. 150. 37-47 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Funabiki, Y. Nagai, H. Kojima, T. Tanaka, S. Yoshida, H. Masuda: "X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato (pyridine) iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases"Inorg.Chim.Acta. 275/276. 222-229 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Funabiki, T. Yamazaki, A. Fukui, T. Tanaka, S. Yoshida: "Oxygenative cleavage of chlorocatechols with molecular oxygen catallyzed by nonheme iron(III) complees and its relevance to chlorocatechol dioxygenases"Angew.Chem.Intern.Ed.Eng.. 37. 513-515 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Funabiki, T. Yokomizo, S. Suzuki, S. Yoshida: "ortho-Hydroxylation of 4-Tert-Butylphenol by Nonheme Iron(III) Complexes as a Functional Model Reaction for Tyrosine Hydroxylase"J.Chem.Soc., Chem.Commun.. 151-152 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Funabiki (Ed.): "Oxygenases and Model Systems"Kluwer Academic Publishers. 1-393 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Ryo Yamahara: "(Catecholato) iron (III) complexes with tetradentate tripodal ligands containing substituted phenol and pyridine units as structural and functional model complexes for the catechol-baound intermediate of intradiol-cleaving catechol dioxygenases"Inorg. Chim. Acta,. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] Takuzo Funabiki: "Mechanism of Oxygenative Cleavage of Catechols by Nonheme Iron Complexes in Relevance to Catechol Dioxygenases Studied by Quantum Chemical Calculations"J. Mol. Cat. A.. 150. 37-47 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takashi Yamamoto: "Structural Analysis of Iron and Manganese Species in Iron- and Manganese - Sulfated Zirconia"J. Phys. Chem. B. 103. 2385-2393 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Tsunehiro Tanaka: "Photocatalytic Oxidation of Alkane at a Steady Rate over Alkali-Ion-Modified Vanadium Oxide Supported on Silica"Catal. Today. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] Takuzo Funabiki: "X-ray Crystallographic and absorption spectroscopic analyses of structures of catecholato (pyridine) iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases" Inorg.Chim.Acta. 275-276. 222-229 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatcchols with molecular oxygen catalyzed by nonheme iron (III) complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern. Ed. Eng.37. 513-515 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 船引卓三: "鉄錯体による酵素類似型酸素化反応" 触媒. 40. 310-317 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Sakae Takenaka: "Structures of Molybdenum Specics in Silica-Supported Molybdenum Oxide and Alkali-Ion-Modified Silica-Supported Molybdenum Oxide" J.Phys.Chem.B. 102. 2906-2909 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yoshiumi Kohno: "Identification and Reactivity of a Surface Intermediate in the Photoreduction of CO2 with H2 over ZrO2" J.Chem.Soc.,Faraday Trans.94. 1875-1880 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Sakae Takenaka: "Effect of Alkali Ion Addition to Silica-supported Molybdenum Oxide on Photocatalysis : Photooxidation of Propane and Propenc,and Photo-Assisted Mctathesis Reaction of Propene" J.Chem.Soc.,Faraday Trans.94. 695-670 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takuzo Funabiki: "X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato (pyridine) iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases" Inorg.Chim.Acta. (in press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron (III) complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern.Ed.Eng.,. 37. 513-515 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takuzo Funabiki: "ortho-Hydroxylation of 4-Tert-Butylphenol by Nonheme Iron (III) Complexes as a Functional Model Reaction for Tyrosine Hydroxylase" J.Chem.Soc.,Chem.Commum.151-152 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Sakae Takenaka: "Structure of Active Species in Alkali-Ion-Modified Silica-Supported Vanadium Oxide" J.Phys.Chem.B. 101. 9035-9045 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Yoshida: "Epoxidation of Propene by Gaseous Oxygen over Silica and Mg-loaded Silica under Photoirradiation" J.Catal.171. 351-357 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Sakae Takenaka: "Reaction Mechanism of Photooxidation of Propane over Alkali-Ion-Modified Silica-Supported Vanadium Pentaoxide under Irradiation by Visible Light" J.Chem.Soc.,Faraday Trans.93. 4151-4158 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenases and Model Systems." Kluwer Academic Publishers,Dordrecht/Boston/London,393 (1997)

    • Related Report
      1997 Annual Research Report

URL: 

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

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi