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Formation and characterization of a reactive chromium(V)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions
http://hdl.handle.net/2241/00123648
http://hdl.handle.net/2241/001236481cdace87-b2ec-4100-8378-88f12384cc7e
名前 / ファイル | ライセンス | アクション |
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CS_6-2.pdf (1.5 MB)
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Item type | Journal Article(1) | |||||
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公開日 | 2015-03-10 | |||||
タイトル | ||||||
タイトル | Formation and characterization of a reactive chromium(V)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源 | http://purl.org/coar/resource_type/c_6501 | |||||
タイプ | journal article | |||||
著者 |
Kotani, Hiroaki
× Kotani, Hiroaki× Kaida, Suzue× Ishizuka, Tomoya× Sakaguchi, Miyuki× Ogura, Takashi× Shiota, Yoshihito× Yoshizawa, Kazunari× Kojima, Takahiko |
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著者別名 |
小谷, 弘明
× 小谷, 弘明× 石塚, 智也× 小島, 隆彦 |
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抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | A mononuclear Cr(V)–oxo complex, [CrV(O)(6-COO−-tpa)](BF4)2 (1; 6-COO−-tpa = N,N-bis(2-pyridylmethyl)-N-(6-carboxylato-2-pyridylmethyl)amine) was prepared through the reaction of a Cr(III) precursor complex with iodosylbenzene as an oxidant. Characterization of 1 was achieved using 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 analysis of the electron-transfer (ET) equilibrium between 1 and a one-electron donor, [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine). The reorganization energy (λ) 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 smaller λ value in comparison with that of an Fe(IV)–oxo complex (2.37 eV) is caused by the small structural change during ET due to the dπ character of the electron-accepting LUMO of 1. When benzyl alcohol derivatives (R-BA) with different oxidation potentials were employed as substrates, corresponding aldehydes were obtained as the 2e−-oxidized products in moderate yields as determined from 1H NMR and GC-MS measurements. One-step UV-vis spectral changes were observed in the course of the oxidation reactions of BA derivatives by 1 and a kinetic isotope effect (KIE) was observed in the oxidation reactions for deuterated BA derivatives at the benzylic position as substrates. These results indicate that the rate-limiting step is a concerted proton-coupled electron transfer (PCET) from substrate to 1. In sharp contrast, in the oxidation of trimethoxy-BA (Eox = 1.22 V) by 1, trimethoxy-BA radical cation was observed by UV-vis spectroscopy. Thus, it was revealed that the mechanism of the oxidation reaction changed from one-step PCET to stepwise ET–proton transfer (ET/PT), depending on the redox potentials of R-BA. | |||||
書誌情報 |
Chemical science 巻 6, 号 2, p. 945-955, 発行日 2015-02 |
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ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 2041-6520 | |||||
書誌レコードID | ||||||
収録物識別子タイプ | NCID | |||||
収録物識別子 | AA12555653 | |||||
DOI | ||||||
識別子タイプ | DOI | |||||
関連識別子 | 10.1039/C4SC02285H | |||||
権利 | ||||||
権利情報 | © The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. | |||||
著者版フラグ | ||||||
値 | author | |||||
出版者 | ||||||
出版者 | The Royal Society of Chemistry |