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2014 年度 実績報告書

非ヘム高原子価マンガンオキソ錯体の反応性に及ぼす金属イオンの効果

研究課題

研究課題/領域番号 14J00541
研究機関大阪大学

研究代表者

尹 熙晶  大阪大学, 工学研究科, 特別研究員(DC2)

研究期間 (年度) 2014-04-25 – 2016-03-31
キーワードMetal-Oxo Complexes / Enzyme Model / Lewis Acid Effect / Hydride Transfer / Electron Transfer
研究実績の概要

During 2014 research, extended work of Mn(IV)-oxo complexes has been mainly focused. The published result is ‘the mechanism of hydride transfer from NADH analogues to an nonheme Mn(IV)-oxo complex’ on Chemical Communication in 2014. Mn(IV)-oxo complex is compared with that of hydride transfer to an Fe(IV)-oxo complex revealing the reaction proceeds via a rate-determining electron transfer with no deuterium kinetic isotope effect. Therefore, a charge-transfer complex formed between the Mn(IV)-oxo complex and NADH analogues is clarified in the hydride transfer reaction. Also, The factors that tune the redox reactivity of the oxo intermediates were thoroughly investigated especially with the effects of proton. Diprotonated nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+-(HOTf)2, were synthesized by adding HOTf and were characterized by various spectroscopic methods. The fundamental electron-transfer properties of [(L)MnIV(O)]2+-(HOTf)2 have also been investigated to compare the reactivities with OAT and HAT reactions.

現在までの達成度 (区分)
現在までの達成度 (区分)

2: おおむね順調に進展している

理由

I have been carrying on multiple projects, of course, some of them resulted with published papers and some of them is not. First of all, I have successfully summarized my work on Hydride Transfer by Manganese(IV)-oxo complexes and it appeared on RSC Chemical Communications. In addition, Proton effect on Manganese(IV)-oxo complexes was a bit complicated, but recently it was accepted at RSC Chemical Science. I am proud of such a result for a year and hope that it will be continuously studied for next another year.

今後の研究の推進方策

Currently i have on going research on Lewis acid effect on Manganese(IV)-oxo complexes combining with water effect for that matter. So far, interesting key data has been obtained and i am certain that it will be successfully finished. In addition, I have found very interesting data on photo-irradiated metal complexes. It seems challenging but i am happy to be the pioneer of researching of very undiscovered area.

  • 研究成果

    (4件)

すべて 2015 2014

すべて 雑誌論文 (2件) (うち査読あり 2件、 オープンアクセス 2件、 謝辞記載あり 2件) 学会発表 (2件)

  • [雑誌論文] Tuning the Reactivity of Mononuclear Nonheme Manganese(IV)-Oxo Complexes by Triflic Acid2015

    • 著者名/発表者名
      Junying Chen, Heejung Yoon, Yong-Min Lee, Mi Sook Seo, Ritimukta Sarangi, Shunichi Fukuzumi and Wonwoo Nam
    • 雑誌名

      Chemical Science

      巻: no page ページ: -

    • DOI

      10.1039/C5SC00535C

    • 査読あり / オープンアクセス / 謝辞記載あり
  • [雑誌論文] Hydride Transfer from NADH analogues to nonheme manganese(IV)-oxo complexes via rate-determining electron transfer2014

    • 著者名/発表者名
      Heejung Yoon, Yong-Min Lee, Wonwoo Nam and Shunichi Fukuzumi
    • 雑誌名

      Chemical Communications

      巻: 50 ページ: 12944-12946

    • DOI

      10.1039/C4CC05313C

    • 査読あり / オープンアクセス / 謝辞記載あり
  • [学会発表] Protonated Mononuclear Nonheme Manganese(IV)-Oxo Complexes with Much Enhanced Oxidation Capacity2015

    • 著者名/発表者名
      Heejung Yoon, Yong-Min Lee, Wonwoo Nam and Shunichi Fukuzumi
    • 学会等名
      日本化学会第95回春季年会
    • 発表場所
      Nihon University
    • 年月日
      2015-03-27 – 2015-03-27
  • [学会発表] Hydride Transfer form NADH analogues to a Nonheme Manganese(IV)-oxo Complex via Rate-Determining Electron Transfer2014

    • 著者名/発表者名
      Heejung Yoon, Yong-Min Lee, Wonwoo Nam and Shunichi Fukuzumi
    • 学会等名
      第47回酸化反応討論会
    • 発表場所
      Kumamoto University
    • 年月日
      2014-11-14 – 2014-11-14

URL: 

公開日: 2016-06-01  

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