Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Nozomi Mihara, Yasuyuki Yamada, Hikaru Takaya, Yasutaka Kitagawa, Kazunobu Igawa, Katsuhiko Tomooka, Hiroshi Fujii, Kentaro Tanaka

研究成果: ジャーナルへの寄稿記事

4 引用 (Scopus)

抄録

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+ , which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H 2 O 2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS 4− ) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS 4− to 3 5+ enhanced the catalytic activity.

元の言語英語
ページ(範囲)3369-3375
ページ数7
ジャーナルChemistry - A European Journal
25
発行部数13
DOI
出版物ステータス出版済み - 3 1 2019

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Ethane
Complexation
Dimers
Iron
Oxidation
Alkanes
Porphyrins
Paraffins
Catalysts
Catalyst activity
Rotaxanes
Coulomb interactions
Chemical activation
Temperature
tetraphenylporphine sulfonate

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

これを引用

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer. / Mihara, Nozomi; Yamada, Yasuyuki; Takaya, Hikaru; Kitagawa, Yasutaka; Igawa, Kazunobu; Tomooka, Katsuhiko; Fujii, Hiroshi; Tanaka, Kentaro.

:: Chemistry - A European Journal, 巻 25, 番号 13, 01.03.2019, p. 3369-3375.

研究成果: ジャーナルへの寄稿記事

Mihara, Nozomi ; Yamada, Yasuyuki ; Takaya, Hikaru ; Kitagawa, Yasutaka ; Igawa, Kazunobu ; Tomooka, Katsuhiko ; Fujii, Hiroshi ; Tanaka, Kentaro. / Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer. :: Chemistry - A European Journal. 2019 ; 巻 25, 番号 13. pp. 3369-3375.
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