A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character

Yoshihiro Shimoyama, Tomoya Ishizuka, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Kaoru Mieda, Takashi Ogura, Toshihiro Okajima, Shunsuke Nozawa, Takahiko Kojima

研究成果: ジャーナルへの寄稿記事

11 引用 (Scopus)

抄録

Proton-coupled electron-transfer oxidation of a RuII−OH2complex, having an N-heterocyclic carbene ligand, gives a RuIII−O.species, which has an electronically equivalent structure of the RuIV=O species, in an acidic aqueous solution. The RuIII−O.complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru−O bond showed a lower-energy Raman scattering at 732 cm−1and the Ru−O bond length was estimated to be 1.77(1) Å. The RuIII−O.complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C−H abstraction from the formyl group by the RuIII−O.complex bearing a strong radical character as the active species.

元の言語英語
ページ(範囲)14041-14045
ページ数5
ジャーナルAngewandte Chemie - International Edition
55
発行部数45
DOI
出版物ステータス出版済み - 1 1 2016

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Bearings (structural)
Ruthenium
Oxidation
Benzoic Acid
Benzoic acid
Bond length
Discrete Fourier transforms
Protons
Raman scattering
Ligands
Derivatives
Electrons
Substrates

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

これを引用

A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character. / Shimoyama, Yoshihiro; Ishizuka, Tomoya; Kotani, Hiroaki; Shiota, Yoshihito; Yoshizawa, Kazunari; Mieda, Kaoru; Ogura, Takashi; Okajima, Toshihiro; Nozawa, Shunsuke; Kojima, Takahiko.

:: Angewandte Chemie - International Edition, 巻 55, 番号 45, 01.01.2016, p. 14041-14045.

研究成果: ジャーナルへの寄稿記事

Shimoyama, Y, Ishizuka, T, Kotani, H, Shiota, Y, Yoshizawa, K, Mieda, K, Ogura, T, Okajima, T, Nozawa, S & Kojima, T 2016, 'A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character', Angewandte Chemie - International Edition, 巻. 55, 番号 45, pp. 14041-14045. https://doi.org/10.1002/anie.201607861
Shimoyama, Yoshihiro ; Ishizuka, Tomoya ; Kotani, Hiroaki ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Mieda, Kaoru ; Ogura, Takashi ; Okajima, Toshihiro ; Nozawa, Shunsuke ; Kojima, Takahiko. / A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character. :: Angewandte Chemie - International Edition. 2016 ; 巻 55, 番号 45. pp. 14041-14045.
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abstract = "Proton-coupled electron-transfer oxidation of a RuII−OH2complex, having an N-heterocyclic carbene ligand, gives a RuIII−O.species, which has an electronically equivalent structure of the RuIV=O species, in an acidic aqueous solution. The RuIII−O.complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru−O bond showed a lower-energy Raman scattering at 732 cm−1and the Ru−O bond length was estimated to be 1.77(1) {\AA}. The RuIII−O.complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C−H abstraction from the formyl group by the RuIII−O.complex bearing a strong radical character as the active species.",
author = "Yoshihiro Shimoyama and Tomoya Ishizuka and Hiroaki Kotani and Yoshihito Shiota and Kazunari Yoshizawa and Kaoru Mieda and Takashi Ogura and Toshihiro Okajima and Shunsuke Nozawa and Takahiko Kojima",
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AU - Shimoyama, Yoshihiro

AU - Ishizuka, Tomoya

AU - Kotani, Hiroaki

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Mieda, Kaoru

AU - Ogura, Takashi

AU - Okajima, Toshihiro

AU - Nozawa, Shunsuke

AU - Kojima, Takahiko

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N2 - Proton-coupled electron-transfer oxidation of a RuII−OH2complex, having an N-heterocyclic carbene ligand, gives a RuIII−O.species, which has an electronically equivalent structure of the RuIV=O species, in an acidic aqueous solution. The RuIII−O.complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru−O bond showed a lower-energy Raman scattering at 732 cm−1and the Ru−O bond length was estimated to be 1.77(1) Å. The RuIII−O.complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C−H abstraction from the formyl group by the RuIII−O.complex bearing a strong radical character as the active species.

AB - Proton-coupled electron-transfer oxidation of a RuII−OH2complex, having an N-heterocyclic carbene ligand, gives a RuIII−O.species, which has an electronically equivalent structure of the RuIV=O species, in an acidic aqueous solution. The RuIII−O.complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru−O bond showed a lower-energy Raman scattering at 732 cm−1and the Ru−O bond length was estimated to be 1.77(1) Å. The RuIII−O.complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C−H abstraction from the formyl group by the RuIII−O.complex bearing a strong radical character as the active species.

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