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金属イオン共役電子移動による高原子価金属オキソ錯体の水の酸化触媒活性制御

Research Project

Project/Area Number 12J02902
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

朴 ジュン (2012, 2014)  大阪大学, 大学院工学研究科, 特別研究員(PD)

朴 ジユン (2013)  大阪大学, 大学院工学研究科, 特別研究員(DC1)

Project Period (FY) 2012 – 2014
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥3,300,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2013: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2012: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsElectron Transfer / Lewis Acid / Epoxidation / Unification / C-H Bond Cleavage / Sulfoxidation / C-H結合開裂 / 電子移動 / 酸効果
Outline of Annual Research Achievements

We report efficient epoxidation of styrene derivatives by a nonheme iron(IV)-oxo complex, [(N4Py)Fe^<IV>(O)]^<2+>(N4Py = N, N-bis(2-pyridylmethyl)-N- bis(2-pyridyl)methylamine) with trilflic acid (HOTf). No oxidation of styrene derivatives by [(N4Py)Fe^<IV>(O)]^<2+>(N4Py = N, N-bis(2-pyridylmethyl)-N-bis(2-pyridyl) methylamine) occurred in acetonitrile at 298 K, whereas efficient epoxidation of styrene derivatives was made possible by the presence of triflic acid (HOTf) via proton-coupled electron transfer (PCET) from styrene derivatives to the diprotonated species of [(N4Py)Fe^<IV>(O)]^<2+> with HOTf. Logarithms of the first-order rate constants of HOTf-promoted expoxidation of all styrene derivatives with [(N4Py)Fe^<IV>(O)]^<2+> and PCET from electron donors in the precursor complexes exhibit a remarkably unified correlation with the driving force of PCET in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes are taken into account. The same PCET driving force dependence is obtained for the first-order rate constants of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)Fe^<IV>(O)]^<2+> and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)Fe^<IV>(O)]^<2+> in the precursor complexes. Thus, HOTf-promoted epoxidation of styrene derivatives by [(N4Py)Fe^<IV>(O)]^<2+> proceeds via the rate-determining electron transfer from styrene derivatives to the diprotonated species of [(N4Py)Fe^<IV>(O)]^<2+> as the case of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)Fe^<IV>(O)]^<2+> and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)Fe^<IV>(O)]^<2+>.

Current Status of Research Progress
Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

All of oxidation reaction which occur by electron transfer from organic substrates to nonheme iron(IV)-oxo in the presence of Lewis acid can be unified in Marcus theory. With Lewis and Bronsted acid, such as metal ion and HOTf, effect on oxidation reaction by non-heme iron(IV)-oxo well studied in our system.

Strategy for Future Research Activity

Lewis acids, such as redox inactive metal ion and proton, can promote oxidation reaction of organic substrate by nonheme iron(IV)-oxo complex via electron transfer. Huge enhancement came from precursor complex formation of metal ion-bounded or protomated nonheme iron(IV)-oxo and substrate. By using this super reactive species, the other oxidation reaction can be done which never has been studied by nonheme high-valent metal-oxo complex, not only with iron but also the other metals, Co, Cu, Cr and so on.

Report

(3 results)
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (9 results)

All 2014 2013 2012

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (6 results)

  • [Journal Article] Unified View of Oxidative C-H Bond Cleavage and Sulfoxidation by a Nonheme Iron (IV)_Oxo Complex via Lewis Acid-Promoted Electron Transfer2014

    • Author(s)
      Jiyun Park ; Yuma Morimoto ; Yong-min Lee ; Wonwoo Nam ; Shunichi Fukuzumi
    • Journal Title

      Inorganic Chemistry

      Volume: 53 Issue: 7 Pages: 3618-3628

    • DOI

      10.1021/ic403124u

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bransted Acid-Promoted C-H Bond Cleavage via Electron Transfer from Toluene Derivatives to a Protonated Nonheme lron(IV)-OXo Complex with No Kinetic Isotope Effect2013

    • Author(s)
      Jiyun Park
    • Journal Title

      Journal of America Chemical Society

      Volume: 135 Issue: 13 Pages: 5052-5061

    • DOI

      10.1021/ja311662w

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanistic Borderline of One-Step Hydrogen Atom Transfer Versus Stepwise Sc^<3+>-Coupled Electron Transfer from Benzyl Alcohol Derivatives to a Non-Heme Iron(IV)-Oxo Complex2012

    • Author(s)
      Yuma Morimoto; Jiyun Park; Tomoyoshi Suenobu; Yong-min Lee; Wonwoo Nam; Shunichi Fukuzumi
    • Journal Title

      Inorganic Chemistry

      Volume: 51 Issue: 18 Pages: 10025-10036

    • DOI

      10.1021/ic3016723

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] 酸存在下の非ヘム鉄四価オキソ錯体によるオレフインの酸化反応におけるプロトン共役電子移動機構2014

    • Author(s)
      Jiyun Park
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学、名古屋
    • Year and Date
      2014-03-27
    • Related Report
      2013 Annual Research Report
  • [Presentation] Triflic Acid-Promoted Olefin Oxidation by a Nonheme Iron (IV)-Oxo Complex via Proton-Coupled Electron Transfer2013

    • Author(s)
      Jiyun Park
    • Organizer
      The 4^<th> Asian Coordination Chemistry Conference
    • Place of Presentation
      Jeju, Korea
    • Year and Date
      2013-11-05
    • Related Report
      2013 Annual Research Report
  • [Presentation] Unification of the Reactivity of Non-Heme Iron (IV)-Oxo on Metal- and Proton-Coupled Electron Transfer2013

    • Author(s)
      Jiyun Park
    • Organizer
      The International Conference on Biological Inorgan is Chemistry (IcBIC 16)
    • Place of Presentation
      Grenoble, France
    • Year and Date
      2013-07-23
    • Related Report
      2013 Annual Research Report
  • [Presentation] 非ヘム鉄(IV)オキソ錯体によるスルホキシル化およびc-H結合活性化における金属イオン共役電子移動とプロトン共役電子移動の統一的理解2013

    • Author(s)
      Jiyun Park
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学びわ湖草津キャンパス、滋賀
    • Year and Date
      2013-03-22
    • Related Report
      2012 Annual Research Report
  • [Presentation] Remarkable Enhancement of C-H Activation via Bransted Acid-Promoted Electron Transfer from Toluene and Derivatives to a Non-Heme Iron(IV)-Oxo Complex2012

    • Author(s)
      Jiyun Park
    • Organizer
      The 6th Asian Biological Inorganic Chemistry Conference
    • Place of Presentation
      Polytechnic University, Hong Kong
    • Year and Date
      2012-11-06
    • Related Report
      2012 Annual Research Report
  • [Presentation] Remarkable Enhancement of C-H Activation via Brensted Acid-Promoted Electron Transfer from Toluene and Derivatives to a Non-Heme lron(IV)-Oxo Complex2012

    • Author(s)
      Jiyun Park
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      富山大学,富山
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report

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Published: 2013-04-25   Modified: 2024-03-26  

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