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

Development of a highly reactive high-valent metal-oxo species and the oxidation catalysis

Research Project

Project/Area Number 24750052
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

HIROAKI Kotani  筑波大学, 数理物質系, 助教 (10610743)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2012: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywordsオキソ錯体 / 電子移動 / 水素引き抜き反応 / 酸化反応 / クロム(V)-オキソ錯体 / 基質酸化反応 / 水素原子移動 / 高原子価オキソ錯体 / クロム / 酸化還元電位 / 反応機構
Research Abstract

The formation of a mononuclear Cr(V)-oxo (1) complex was confirmed by ESI-MS spectrometry, electron paramagnetic resonance, UV-vis, and resonance Raman spectroscopies. The reduction potential (Ered) of 1 was determined to be 1.23 V vs SCE in acetonitrile based on the analysis of electron-transfer (ET) equilibrium between 1 and a one-electron donor. Reorganization energy of 1 was also determined to be 1.03 eV in ET reactions from phenol derivatives to 1 on the basis of the Marcus theory of ET. The reaction of 1 with various benzyl alcohol derivatives (BA) afforded corresponding 2e-oxidized products despite the higher oxidation potentials. In the case of trimethoxy-BA (Eox = 1.23 V) as a substrate, trimethoxy-BA radical cation was observed in the course of the reaction by UV-vis spectroscopy. It was revealed that the rate-determining step of the oxidation reaction was changed from one-step HAT to stepwise electron-proton transfer, depending on the redox potential of BA derivatives.

Report

(3 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • Research Products

    (9 results)

All 2014 2013 2012 Other

All Presentation (8 results) Remarks (1 results)

  • [Presentation] モノアニオン性配位子を有するクロム(V)-オキソ錯体の電子移動特性2014

    • Author(s)
      改田鈴枝, 小谷弘明, 石塚智也, 小島隆彦
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知・名古屋大学
    • Year and Date
      2014-03-27
    • Related Report
      2013 Final Research Report
  • [Presentation] モノアニオン性配位子を有するクロム(V)-オキソ錯体の電子移動特性2014

    • Author(s)
      改田鈴枝、小谷弘明、石塚智也、小島隆彦
    • Organizer
      日本化学会第94春季年会(2014)
    • Place of Presentation
      名古屋大学(名古屋)
    • Related Report
      2013 Annual Research Report
  • [Presentation] CPET過程を伴う有機化合物酸化反応におけるクロム(V)-オキソ錯体の反応性の制御2013

    • Author(s)
      改田鈴枝, 小谷弘明, 石塚智也, 小島隆彦
    • Organizer
      第46回酸化反応討論会
    • Place of Presentation
      茨城・筑波大学
    • Year and Date
      2013-11-15
    • Related Report
      2013 Final Research Report
  • [Presentation] 高い反応性を有するクロム(V)-オキソ錯体の同定とベンジルアルコール類酸化反応の機構解明2013

    • Author(s)
      改田鈴枝, 小谷弘明, 石塚智也, 小島隆彦
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀・立命館大学
    • Year and Date
      2013-03-22
    • Related Report
      2013 Final Research Report
  • [Presentation] CPET過程を伴う有機化合物酸化反応におけるクロム(V)-オキソ錯体の反応性の制御2013

    • Author(s)
      改田鈴枝、小谷弘明、石塚智也、小島隆彦
    • Organizer
      第46回酸化反応討論会
    • Place of Presentation
      筑波大学(つくば)
    • Related Report
      2013 Annual Research Report
  • [Presentation] 高い反応性を有するクロム(V)-オキソ錯体の同定とベンジルアルコール類酸化反応の機構解明2013

    • Author(s)
      改田鈴枝・小谷弘明・石塚智也・小島隆彦
    • Organizer
      日本化学会第93春季年会(2013)
    • Place of Presentation
      立教大学
    • Related Report
      2012 Research-status Report
  • [Presentation] モノアニオン性配位子を有するクロム(V)-オキソ錯体の反応性2012

    • Author(s)
      改田鈴枝, 小谷弘明, 石塚智也, 小島隆彦
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      岡山・岡山理科大学
    • Year and Date
      2012-09-17
    • Related Report
      2013 Final Research Report
  • [Presentation] モノアニオン性配位子を有するクロム(V)-オキソ錯体の反応性2012

    • Author(s)
      改田鈴枝・小谷弘明・石塚智也・小島隆彦
    • Organizer
      錯体化学会第62回討論会
    • Place of Presentation
      富山大学
    • Related Report
      2012 Research-status Report
  • [Remarks]

    • URL

      http://www.chem.tsukuba.ac.jp/kojima/

    • Related Report
      2013 Final Research Report

URL: 

Published: 2013-05-31   Modified: 2019-07-29  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi