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Synthesis, electrochemical investigation and EPR spectroscopy of a reversible four-stage redox system based on mesoionic 5,5'-azinobis(1,3-diphenyltetrazole) and related mesoionic compounds
https://nitech.repo.nii.ac.jp/records/4613
https://nitech.repo.nii.ac.jp/records/4613148c55bc-4bd3-47bd-87ec-5a1f006aa3d4
| 名前 / ファイル | ライセンス | アクション |
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本文_fulltext (374.2 kB)
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J. Chem. Soc., Perkin Trans. 2, 1999, 985-995 -Reproduced by permission of The Royal Society of Chemistry (RSC)
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| Item type | 学術雑誌論文 / Journal Article(1) | |||||||||||||||||||||||||||
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| 公開日 | 2012-11-06 | |||||||||||||||||||||||||||
| タイトル | ||||||||||||||||||||||||||||
| タイトル | Synthesis, electrochemical investigation and EPR spectroscopy of a reversible four-stage redox system based on mesoionic 5,5'-azinobis(1,3-diphenyltetrazole) and related mesoionic compounds | |||||||||||||||||||||||||||
| 言語 | en | |||||||||||||||||||||||||||
| 言語 | ||||||||||||||||||||||||||||
| 言語 | eng | |||||||||||||||||||||||||||
| 資源タイプ | ||||||||||||||||||||||||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||||||||||||||||||||||||
| 資源タイプ | journal article | |||||||||||||||||||||||||||
| 著者 |
Araki, Shuki
× Araki, Shuki
× Yamamoto, Kaori
× Inoue, Tomoko
× Fujimoto, Koji
× Yamamura, Hatsuo
× Kawai, Masao
× Butsugan, Yasuo
× Zhou, Jinkui
× Eichhorn, Emerich
× Rieker, Anton
× Huber, Martina
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| 著者別名 | ||||||||||||||||||||||||||||
| 姓名 | 荒木, 修喜 | |||||||||||||||||||||||||||
| 著者別名 | ||||||||||||||||||||||||||||
| 姓名 | 山村, 初雄 | |||||||||||||||||||||||||||
| 書誌情報 |
en : Journal of the Chemical Society. Perkin transactions 2 巻 1999, 号 5, p. 985-995, 発行日 1999-01-01 |
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| 出版者 | ||||||||||||||||||||||||||||
| 出版者 | Royal Society of Chemistry | |||||||||||||||||||||||||||
| 言語 | en | |||||||||||||||||||||||||||
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| 収録物識別子タイプ | ISSN | |||||||||||||||||||||||||||
| 収録物識別子 | 0300-9580 | |||||||||||||||||||||||||||
| item_10001_source_id_32 | ||||||||||||||||||||||||||||
| 収録物識別子タイプ | NCID | |||||||||||||||||||||||||||
| 収録物識別子 | AA00695145 | |||||||||||||||||||||||||||
| 出版タイプ | ||||||||||||||||||||||||||||
| 出版タイプ | VoR | |||||||||||||||||||||||||||
| 出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||||||||||||||||||||||||
| item_10001_relation_34 | ||||||||||||||||||||||||||||
| 関連タイプ | isIdenticalTo | |||||||||||||||||||||||||||
| 識別子タイプ | DOI | |||||||||||||||||||||||||||
| 関連識別子 | http://dx.doi.org/10.1039/A809386E | |||||||||||||||||||||||||||
| 関連名称 | 10.1039/A809386E | |||||||||||||||||||||||||||
| 内容記述 | ||||||||||||||||||||||||||||
| 内容記述タイプ | Other | |||||||||||||||||||||||||||
| 内容記述 | Mesoionic 5,5′-azinobis(1,3-diphenyltetrazole) 1 was prepared, and its chemical oxidation gave stable crystals of the corresponding radical cation 1?+ and dication 12+, which reversibly gave back azine 1 on reduction with zinc. Electrochemical investigations of 1 using cyclovoltammetry and differential pulse voltammetry in pyridine (Py) or dichloromethane (DCM) also revealed the two reversible successive one-electron oxidations leading to dication 12+via radical cation 1?+, both of which can be reduced to the neutral state 1. In the cathodic process, 1 was reduced by two consecutive one-electron transfers at only slightly different potentials up to the corresponding dianion 12? which could be re-oxidized to the neutral state; thus constituting a reversible four-stage redox system. Radical cation 1?+ and anion 1?- were characterized by EPR spectroscopy. In order to get more insights into the spin-density distribution of 1?+, the bis- and tetra-15N-labelled species 1a?+, 1b?+ and 1c?+ were synthesized and investigated by EPR and 15N as well as 14N ENDOR spectroscopy, revealing that the largest N hyperfine coupling constants are due to the nitrogen atoms of the central bridge. According to 1H ENDOR there seems to be a small coupling with the protons of both phenyl rings which cannot be resolved in the EPR spectrum.The electrochemical properties of the related mesoionic compounds 5-10 were also investigated in Py or DCM solutions. In the cathodic process, a reduction peak of 9 and 10 was observed due to their reversible one-electron reduction to the corresponding radical anions. The radical obtained on reduction of 10 was characterized by EPR spectroscopy. On the other hand, 5-8 can be reduced by a formal two-electron transfer up to the corresponding dianions which are re-oxidizable to the neutral state. In the anodic process, 9/10 undergo irreversible one-electron oxidations whereas 5/6 (in DCM) and 7/8 (in Py) experience reversible or irreversible step by step two-electron oxidations leading to the dications. In Py the oxidation products of 5/6 react to further species revealing two more oxidation and several rereduction peaks. On the other hand, the oxidation products of 7/8 are instable in DCM (one main oxidation and rereduction peak). The electrochemical data are discussed in terms of delocalization in the cations and conjugation in the dications. | |||||||||||||||||||||||||||
| 言語 | en | |||||||||||||||||||||||||||
