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Synthesis and Control of Functions of Metal Complexes Having Oxygen Active Species

Research Project

Project/Area Number 16350030
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionKanazawa University

Principal Investigator

SUZUKI Masatatsu  Graduate School of Natural Science and Technology, Professor, 自然科学研究科, 教授 (20091390)

Co-Investigator(Kenkyū-buntansha) FUJINAMI Shuhei  Graduate School of Natural Science and Technology, Associate Professor, 自然科学研究科, 助教授 (10115272)
FURUTACHI Hideki  Graduate School of Natural Science and Technology, Assistant Professor, 自然科学研究科, 助手 (40332663)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥15,700,000 (Direct Cost: ¥15,700,000)
Fiscal Year 2006: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2005: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2004: ¥8,500,000 (Direct Cost: ¥8,500,000)
KeywordsSynthetic Chemistry / Bioinorganic Chemistry / Peroxo-dicopper(II) / Oxygen active species / Oxidation reactions / C-H bond activation / Peroxo-diiron(III) / Crystal structures / ペルオキソ二核銅錯体 / 二核鉄錯体 / 水酸化反応 / 金属酵素モデル / ヒドロペルオキソ銅(II)錯体 / 水素結合 / 金属錯体 / エポキシ化反応
Research Abstract

The purpose of this project is the development of the peroxo-dicopper(II) and diiron(III) complexes as functional models for tyrosinase and toluene monooxygenase.
We have succeeded in synthesis of (μη^2:η^2-peroxo)Cu(II)_2 complexes, [Cu_2(O_2)(R-L)]^<2+> (oxy-R-1: R = H, MeO, t-Bu, and NO_2), where R-L = 1,3-Bis[bis(6-methyl-2pyridylmethyl)aminomethy1]-5-R-benzene, which can perform not only hydroxylation of the m-xylyl linker of R-L, but also epoxidation of styrene via an electrophilic addition of the peroxide to the C=C bond, the latter of which is the first example of the epoxidation of styrene by a discrete (μη^2:η^2-peroxo)Cu(II)_2 species. In addition, oxy-H-1 can oxidize various aliphatic C-H bonds via H-atom abstraction. A linear correlation between log k (the second order rate constants of oxidation) and the bond dissociation energies of the C-H bonds was observed. The results provide new insights into the reactivity of (μη^2:η^2 peroxo) Cu(II)_2 complexes.
(μ-Peroxo)diiron(III) Complex: A Functional Model for Toluene Monooxygenase. We have succeeded in synthesis of two types of peroxodiiron(III) complexes, [Fe2(L^<Ph4>)(RCO_2)(O_2)]^<2+> (R = Ph_3C (oxy-1) and Ph (oxy-2)), the former leads to regioselective hydroxylation of a phenyl group of L^<Ph4> and the latter exhibits reversible deoxygenation (L^<Ph4> = N, N, N',N'-tetrakis[(1-methyl-2-pheny1-4-imidazolyl)methy1]-1,3-diamino-2-propanolate). This is the first example of the peroxodiiron(III) complex which is capable of arene hydroxylation. The reactions mimic toluene monooxygenase and hemerythrin reactivity, respectively. They provide new insights into the reactivity of the peroxodiiron(III) complexes having a nitrogen-rich coordination environment like alkane arhydroxylase and hemerythrin.

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (38 results)

All 2007 2006 2005 2004

All Journal Article (34 results) Book (4 results)

  • [Journal Article] Synthesis and Reactivity of (μ-η^2 : η^2-Peroxo)dicopper(II) Complexes with Dinucleating Ligands : Hydroxylation of Xylyl Linker with a NIH Shift2007

    • Author(s)
      T.Matsumoto, M.Suzuki, et al.
    • Journal Title

      Journal of Organometallic Chemistry 692・1-3

      Pages: 111-121

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Regioselective Arene Hydroxylation Mediated by a (μ-Peroxo)diiron(III) Complex : A Functional Model for Toluene Monooxygenase2007

    • Author(s)
      M.Yamashita, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 129・1

      Pages: 2-3

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis and Reactivity of (μ-η2 : η2-Peroxo)dicopper(II) Complexes with Dinucleating Ligands : Hydroxylation of Xylyl Linker with a NIH Shift2007

    • Author(s)
      T.Matsumoto, M.Suzuki, et al.
    • Journal Title

      J. Organometal. Chem. 692-1-3

      Pages: 111-121

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Regioselective Arene Hydroxylation Mediated by a (μ-Peroxo)diiron(III) Complex : A Functional Model for Toluene Monooxygenase2007

    • Author(s)
      M.Yamashita, M.Suzuki, et al.
    • Journal Title

      J. Am. Chem. Soc 129-1

      Pages: 2-3

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Regioselective Arene Hydroxylation Mediated by (μ-Peroxo)diiron(III)Complex : A Functional Model for Toluene Monooxygenase2007

    • Author(s)
      M.Yamashita, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 129・1

      Pages: 2-3

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A Mononuclear Alkylperoxocopper(II) Complex as a Reaction Intermediate in the Oxidation of the Methyl Group of the Supporting Ligand2006

    • Author(s)
      M.Mizuno, M.Suzuki, et al.
    • Journal Title

      Angewandte Chemie International Edition 45・41

      Pages: 6911-6914

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sequential Reaction Intermediates in Aliphatic C-H Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III) Complex2006

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Inorganic Chemistry 45・7

      Pages: 2873-2885

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Intramolecular Arene Hydroxylation versus Intermolecular Olefin Epoxidation by (μ-η^2 : η^2-Peroxo)dicopper(II) Complex Supported by Dinucleating Ligand2006

    • Author(s)
      T.Matsumoto, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 128・12

      Pages: 3874-3875

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A Mononuclear Alkylperoxocopper(II) Complex as a Reaction Intermediate in the Oxidation of the Methyl Group of the Supporting Ligand2006

    • Author(s)
      M.Mizuno, M.Suzuki, et al.
    • Journal Title

      Angew. Chem. Int. Ed. 45:41

      Pages: 6911-6914

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sequential Reaction Intermediates in Aliphatic OH Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III) Complex2006

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Inorg. Chem. 45-7

      Pages: 2873-2885

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Intramolecular Arene Hydroxylation versus Intermolecular Olefin Epoxidation by (μ-η2 : η2-Peroxo)dicopper(II) Complex Supported by Dinucleating Ligand2006

    • Author(s)
      T.Matsumoto, M.Suzuki.et al.
    • Journal Title

      J. Am. Chem. Soc. 128-12

      Pages: 3874-3875

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sequential Reaction Intermediates in Aliphatic C-H Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III)Complex2006

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Inorganic Chemistry 45・7

      Pages: 2873-2885

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A Mononuclear Alkylperoxocopper(II)Complex as a Reaction Intermediate in the Oxidation of the Methyl Group of the Supporting Ligand2006

    • Author(s)
      M.Mizuno, M.Suzuki, et al.
    • Journal Title

      Angewandte Chemie International Edition 45・

      Pages: 6911-6914

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Intramolecular Arene Hydroxylation versus Intermolecular Olefin Epoxidation by (μ-η^2:η^2-Peroxo)dicopper(II) Complex Supported by Dinucleating Ligand2006

    • Author(s)
      T.Matsumoto, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 128(In press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Sequential Reaction Intermediates in Aliphatic C-H Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III) Complex2006

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Inorganic Chemistry 45(In press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Mass Spectrometric and Spectroscopic Studies on Hydrolysis of Phosphoesters by Bis(μ-acetato)-μ-phenolato Dinuclear Metal(II) Complexes (Metal=Mn, Co, Ni, and Zn)2005

    • Author(s)
      R.Jikido, H.Okawa, M.Suzuki, et al.
    • Journal Title

      Bulletin of The Chemical Society of Japan 78・10

      Pages: 1795-1803

    • NAID

      130004151816

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Structure and Dioxygen-reactivity of Copper(I) Complexes Supported by Bis(6-methylpyridin-2-yl-methyl)amine Tridentate Ligands2005

    • Author(s)
      S.Itoh, M.Suzuki, et al.
    • Journal Title

      Journal of Chemical Society, Dalton Transaction 21

      Pages: 3514-3521

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Reversible O-O Bond Cleavage and Formation of a Peroxo Moiety of a Peroxocarbonate Ligand Mediated by an Iron(III) Complex2005

    • Author(s)
      H.Furutachi, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127・13

      Pages: 4550-4551

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Synthesis and Reactivity of a (μ-1, 1-Hydroperoxo)(μ-hydroxo)dicopper(II) Complex : Ligand Hydroxylation by a Bridging Hydroperoxo Ligand2005

    • Author(s)
      K.Itoh, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127・14

      Pages: 5212-5223

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Structural and Spectroscopic Characterization of (μ-Hydroxo or μ-oxo)(μ-peroxo)diiron(III) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins2005

    • Author(s)
      X.Zhang, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127・3

      Pages: 826-827

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Mass Spectrometric and Spectroscopic Studies on Hydrolysis of Phosphoesters by Bis(μ-acetato)-μ-phenolato Dinuclear Metal(II) Complexes (Metal = Mn, Co, Ni, and Zn)2005

    • Author(s)
      R.Jikido, H.Okawa, M.Suzuki, et al.
    • Journal Title

      Bull. Chem. Soc. Jpn 78-10

      Pages: 1795-1803

    • NAID

      130004151816

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Structure and Dioxygen-reactivity of Copper(I) Complexes Supported by Bis(6-methylpyridin-2-yl-methypamine Tridentate Ligands2005

    • Author(s)
      S.Itoh, M.Suzuki, et al.
    • Journal Title

      J. Chem. Soc., Dalton Trans. 21

      Pages: 3514-3521

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reversible 0-0 Bond Cleavage and Formation of a Peroxo Moiety of a Peroxocarbonate Ligand Mediated by an Iron(III)2005

    • Author(s)
      Complex, H.Furutachi, M.Suzuki, et al.
    • Journal Title

      J. Am. Chem. Soc. 127-13

      Pages: 4550-4551

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis and Reactivity of a (μ-1,1-Hydroperoxo)(μ- hydroxo)dicopper(II) Complex : Ligand Hydroxylation by a Bridging Hydroperoxo Ligand2005

    • Author(s)
      K.Itoh, M.Suzuki, et al.
    • Journal Title

      J. Am. Chem. Soc 127-14

      Pages: 5212-5223

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Structural and Spectroscopic Characterization of (μ-Hydroxo or μ-oxo)( μ-peroxo)diiron(III) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins2005

    • Author(s)
      X.Zhang, M.Suzuki, et al.
    • Journal Title

      J. Am. Chem. Soc 127-3

      Pages: 826-827

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis and Reactivity of a (μ-1,1-Hydroperoxo)(μ-hydroxo)dicopper(II) Complex : Ligand Hydroxylation by a Bridging Hydroperoxo Ligand2005

    • Author(s)
      K.Itoh, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127・14

      Pages: 5212-5223

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Mass Spectrometric and Spectroscopic Studies on Hydrolysis of Phosphoesters by Bis(μ-acetato)-μ-phenolato Dinuclear Metal(II) Complexes (Metal=Mn,Co,Ni, and Zn)2005

    • Author(s)
      R.Jikido, H.Okawa, M.Suzuki, et al.
    • Journal Title

      Bulletin of The Chemical Society of Japan 78・10

      Pages: 1795-1803

    • NAID

      130004151816

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Structural and Spectroscopic Characterization of (μ-Hydroxo orμ-oxo)(μ-peroxo)diiron(III) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins2005

    • Author(s)
      X.Zhang, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127

      Pages: 826-882

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis and Reactivity of a (μ-1,1-Hydroperoxo)(μ-hydroxo)dicopper(II) Complex : Ligand Hydroxylation by a Bridging Hydroperoxo Ligand2005

    • Author(s)
      K.Itoh, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127(in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reversible O-O Bond Cleavage and Formation of a Peroxo Moiety of a Peroxocarbonate Ligand Mediated by an Iron(III) Complex2005

    • Author(s)
      H.Furutachi, M.Suzuki, et al.
    • Journal Title

      Journal of American Chemical Society 127(in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Structure and Dioxygen-reactivity of Copper(I) Complexes Supported by Bis(6-methylpyridin-2-y1-methyl)amine Tridentate Ligands2005

    • Author(s)
      S.Itoh, M.Suzuki, et al.
    • Journal Title

      Journal of Chemical Society, Dalton Transaction (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Formation and Characterization of a Bis(m-alkylperoxo)dinickel(II) Complex as a Reaction Intermediate for Oxidation of Methyl Group of Me_2-tpa Ligand to Carboxylate and Alkoxide Ligands2004

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Angewandte. Chemie International Edition 43・25

      Pages: 3300-3303

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Formation and Characterization of a Bis(ralkylperoxo)- dinickel(II) Complex as a Reaction Intermediate for Oxidation of Methyl Group of Me2-tpa Ligand to Carboxylate and Alkoxide Ligands2004

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Angew. Chem. Int. Ed. 43-25

      Pages: 3300-3303

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Formation and Characterization of a Bis(μ-alkylperoxo)dinickel(II) Complex as a Reaction Intermediate for Oxidation of Methyl Group of Me_2-tpa Ligand to Carboxylate and Alkoxide Ligands2004

    • Author(s)
      J.Cho, M.Suzuki, et al.
    • Journal Title

      Angewandte Chemie International Edition 43・25

      Pages: 3300-3303

    • Related Report
      2004 Annual Research Report
  • [Book] 金属錯体最前線2006

    • Author(s)
      鈴木正樹, 山下正廣, 北川進等
    • Total Pages
      4
    • Publisher
      化学同人
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] 生物無機化学2005

    • Author(s)
      鈴木正樹, 増田秀樹, 福住俊一等
    • Total Pages
      47
    • Publisher
      三共出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] 生物無機化学2005

    • Author(s)
      鈴木 正樹, 増田 秀樹, 福住 俊一等
    • Total Pages
      403
    • Publisher
      三共出版
    • Related Report
      2005 Annual Research Report
  • [Book] 実験化学講座22(第5版)2004

    • Author(s)
      4藤波修平, 鈴木 正樹
    • Total Pages
      4
    • Publisher
      丸善 日本化学会編
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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