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New Development of the Coordination Chemistry of Transition Metal-Oxygen Complexes

Research Project

Project/Area Number 08102006
Research Category

Grant-in-Aid for Specially Promoted Research

Allocation TypeSingle-year Grants
Review Section Chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

MORO-OKA Yoshihiko  Research Laboratory of Resources Utilization, Tokyo Institute of Technology, professor, 資源化学研究所, 教授 (70016731)

Co-Investigator(Kenkyū-buntansha) HIKICHI Shiro  Research Laboratory of Resources Utilization, Tokyo Institute of Technology, assistant professor, 資源化学研究所, 助手 (10282857)
FUJISAWA Kiyoshi  Research Laboratory of Resources Utilization, Tokyo Institute of Technology, assistant professor, 資源化学研究所, 助手 (10251670)
AKIRA Munetaka  Research Laboratory of Resources Utilization, Tokyo Institute of Technology, associate professor, 資源化学研究所, 助教授 (50167839)
Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥165,000,000 (Direct Cost: ¥165,000,000)
Fiscal Year 1998: ¥24,000,000 (Direct Cost: ¥24,000,000)
Fiscal Year 1997: ¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 1996: ¥110,000,000 (Direct Cost: ¥110,000,000)
Keywordsoxygen / transition metal complexes / dioxygen complex / metalloprotein / hydrotrispyrazolylborate / oxo species / poly(phenylene oxide) / ヒドロペルオキソ種
Research Abstract

In order to clarify functions and structure of the active sites of oxygenation catalysts and metalloproteins relevant to oxygen transport and oxygenation reactions, systematic synthetic study of transition metal-dioxygen complexes with hydrotrispyrazolylborates, which can easily modify the coordination electronic and steric environment by appropriate substituents, has been carried out. Key findings are as follows
1. Chemistry of high valent bis(μ-oxo) species
Dinuclear μ-η2:η2-dioxygen complexes of nickel and cobalt are converted via O-O cleavage to high valent bis(μ-oxo) species, which are capable of oxygenation of hydrocarbons. The compounds attract much attention due to their relevance to the active species of methane monooxygenase.
2. Oxygen activation on a mononuclear species
The function of metalloproteins containing mononuclear active center such as catechol dioxygenase, which oxidizes aromatics, has been successfully reproduced.
3. Synthesis of dioxygen complexes of second row metals and early transition metals
The target of the synthetic study has been extended to metals which are not involved in metalloproteins, and such study reveals the characteristic aspects of first row metal species found in the proteins.
4. Regioselective oxidative polymerization of phenols
The dicopper-dioxygen complexes prepared by us are found to be active for oxidative polymerization of phenols to give poly(p-phenylene oxide) in a regioselective manner. The result of a bioinorganic study has been applied to an industrial process.
Other aspects such as mononuclear copper-oxygen complexes relevant to copper enzymes and oxidation of aromatics in the absence of dioxygen are also studied.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] S.Hikichi: "Synthesis and Characterization of the Benzoylformato Ferrous Complexes with the Hindered Ttrispyrazolylborate Ligandb as a Structural Model for Mononuclear Non-Heme Irom Enzymes"Inorg.Chem.. 36. 4539-4547 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Akita: "Systematic synthesis of a series of hydroperoxo-、alkylperoxo- and μ-peroxopalladium complexes supported by the hydrotris (3、5-diisopropylpyrazoly) borate ligand"J.Chem.Soc.、Chem.Commun.. 1005-1006 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Ogihara: "Synthesis、Structural Characterization、and Extradiol Oxygenation of Iron-Catecholato Complexes with Hydrotris (pyrazoly) borate Ligands"Inorg.Chem.. 37. 2614-2615 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Hikichi: "Aliphatic C-H Bond Oxygenation by the Co(II)-OOX Species with the Hindered Hydrotris(pyrazoly)borate Ligands (X=Co(II)、Alkyl、H)"J.Am.Chem.Soc.. 120. 4699-4710 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Higashimura: "Highly Regioselective Oxidative Polymrization of 4-Phenoxuphenol to Poly(1、4-phenylene oxide) Catalyene by Tyrosinase Model Complexes"J.Am.Chem.Soc.. 120. 8529-8530 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Hikichi: "First Synthesis and Structural Characterization of Dinuclear M(III) bis (μ-oxo) Complexes of nickel and Cobalt with Hydrotris (pyrazolyl) borate Ligand"J.Am.Chem.Soc.. 120. 10567-10568 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Akita: "Conversion of Molecular Oxygen into a Hydroperoxo Species via Ring Opening Protonation of a Cyclic η^2 -Peroxide Intermediate :"Anfew.Chem.Int.Ed.in Engl.. 38. 3074-3077 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S. Hikichi: "Synthesis and Characterization of the Benzoylformato Ferrous Complexes with the Hindered Ttrispyrazolylborate Ligand as a Structural Model for Mononuclear Non-Heme Iron Enzymes"Inorg. Chem.. 36. 4539 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Akita: "Systematic synthesis of a series of hydroperoxo-, alkylperoxo- and μ-peroxopalladium complexes supported by the hydrotris(3,5-diisopropylpyrazolyl)borate ligand"J. Chem. Soc., Chem. Commun.. 1005 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T. Ogihara: "Synthesis, Structural Characterization, and Extradioi Oxygenation of Iron-Catecholato Complexes with Hydrotris(pyrazolyl)borate Ligands"Inorg. Chem.. 37. 2614 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S. Hikichi: "Aliphatic C-H Bond Oxygenation by the Co(II)-OOX Species with the Hindered Hydrotris(pyrazolyl)borate Ligands (X=Co(II), Alkyl, H)"J. Am. Chem. Soc.. 120. 4699 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H. Higashimura: "Highly Regioselective Oxidative Polymerization of 4-Phenoxyphenol to Poly(1,4-phenylene oxide) Catalyzed by Tyrosinase Model Complexes"J. Am. Chem. Soc.. 120. 8529 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S. Hikichi: "First Synthesis and Structural Characterization of Dinuclear M(III) bis(μ-oxo) Complexes of nickel and Cobalt with Hydrotris(pyrazolyl)borate Ligand"J. Am. Chem. Soc.. 120. 10567 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Akita: "Conversion of Molecular Oxygen into a Hydroperoxo Species via Ring Opening Protonation of a Cyclic ηィイD12ィエD1-Peroxide Intermediate"Angew. Chem. Int. Ed. In Engl.. 38. 3074 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Komatsuzaki: "Dioxygen activation via a novel manganese(II)thiolate complex with hydrotris(3,5-diisopropylpyrazolyl)borate ligand" J.Chem.Soc.,Dalton Trans.511-512 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Akita: "Systematic synthesis of a series of hydroperoxo-,alkylperoxo-and μ-peroxopalladium complexes supported by the hydrotris(3,5-diisopropylpyrazolyl)borate ligand" J.Chem.Soc.,Chem.Commun.1005-1006 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Komatsuzaki: "The First Synthesis and Structural Characterization of Alkylperoxo Complex of Mn(II)" Inorg.Chem.37. 6554-6555 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Ogihara: "Synthesis.Structural Characterization,and Extradiol Oxygenation of Iron-Catecholato Complexes with Hydrotris(pyrazolyl)borate Ligands" Inorg.Chem.37. 2614-2615 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Hikichi: "Aliphatic C-H Bond Oxygenation by the Co(II)-OOX Species with the Hindered Hydrotris(pyrazolyl)borate Ligands(X=Co(II),Alkyl,H)" J.Am.Chem.Soc.120. 4699-4710 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Higashimura: "Highly Regioselective Oxidative Polymrization of 4-Phenoxuphenol to Poly(1,4-phenylene oxide)Catalyzed by Tyrosinase Model Complexes" J.Am.Chem.Soc.120. 8529-8530 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Hikichi: "First Synthesis and Structural Characterization of Dinuclear M(III)bis(μ-oxo)Complexes of nickel and Cobalt with Hydrotris(pyrazolyl)borate Ligand" J.Am.Chem.Soc.120. 10567-10568 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Osawa: "Dimanganese Complexes Bridged with a (μ-X) (μ-Carboxylato) Unit as Models for the Active Site of Manganese Catalase (X=OH, O) or(O_2);" Chem.Lett.919-920 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Fujisawa: "Preparation,Spectroscopic Characterization,and Molecular Structure of Copper(I) Aliphatic Thiolate Complexes" Inorg.Chem.37. 168-169 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Fujisawa: "Two-coordinate Gold(I) Aliphatic Thiolate Complexes" Chem.Lett.167-168 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Hikichi: "Synthesis and Characterization of the Benzoylformato Ferrous Complexes with the Hindered Trispyrazolyborate Ligand as a Structural Model for Mononuclear Non-Heme Iron Enzymes" Inorg.Chem.36. 4539-4547 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Akita: "Synthesis and Structure Dtermination of Rh-diene Complexes : Dependence of the v (B-H) Values on the Hapticity of the Tp^<iPr> ligand(K^2vs.K^3);" Organometallics. 16. 4121-4128 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Komatsuzaki: "Characterization of a Dinuclear Mn (II)(μ-Hydroxo) (μ-Pyrazolato) Complex and Hydrolytic Equilibrium of the Bridging Pyrazollate Ligand" J.Chem.Soc.,Dalton Trans.(in press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Fujisawa: "A Monomeric Zinc Complex Ligated by an Unsymmetric Hydrotris(pyrazoly) borate Containing an OH Group" Chem.Lett.397-398 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Hikichi: "Characterization of a μ-η^2:η^2 Peroxo Dinuclear Co(II) Complex" Inorg.Chem.36. 266-267 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Hikichi: "Synthesis and Characterization of the Benzoylformato Ferrous Complexes with Hindered Tris(pyrazolyl)borate Ligana as a Structural Model for Mononuclear Non-Heme Iron Enzymes" Inorg.Chem.36(in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Ito: "Oxygenases and Model Systems" Kluwer Academic Publishers, 31 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2018-03-28  

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