The effect of π-π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(II)-salen type complex. Comparison with the corresponding Cu(II) complex

Hiromi Oshita, Takashi Suzuki, Kyohei Kawashima, Hitoshi Abe, Fumito Tani, Seiji Mori, Tatsuo Yajima, Yuichi Shimazaki

研究成果: ジャーナルへの寄稿記事

抄録

In order to gain new insights into the effect of the π-π stacking interaction of the indole ring with the phenoxyl radical moiety as seen in the active form of galactose oxidase, we have prepared Ni(ii) complexes of a methoxy substituted salen-type ligand containing a pendent indole ring on the dinitrogen chelate backbone and characterized their one-electron oxidized forms. The X-ray crystal structure analysis and the other physicochemical experiments of the Ni(ii) complex revealed no significant intramolecular interaction of the indole ring with the coordination plane. On the other hand, the X-ray crystal structures of the oxidized Ni(ii) complex exhibited the π-π stacking interaction of the indole ring mainly with one of the two phenolate moieties. While the phenoxyl radical electron was delocalized on the two phenolate moieties in the Ni(ii)-salen coordination plane, the phenolate moiety in close contact with the indole moiety was considered to be the initial oxidation locus, indicating that the indole ring interacted with the phenoxyl radical by π-π stacking. The UV-vis-NIR spectrum of the oxidized Ni(ii) complex with the pendent indole ring was different from that of the complex without the side chain indole ring, but the differences were rather small in comparison with the oxidized Cu(ii)-salen complexes with the π-π stacking interaction of the indole ring. Such differences are due to the electronic structure difference, the localized radical electron on one of the phenolate moieties in the oxidized Cu(ii) complexes being more favorable for the π-π stacking interaction.

元の言語英語
ページ(範囲)12060-12069
ページ数10
ジャーナルDalton Transactions
48
発行部数32
DOI
出版物ステータス出版済み - 1 1 2019

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Nickel
Electrons
Crystal structure
Galactose Oxidase
indole
disalicylaldehyde ethylenediamine
phenoxy radical
X rays
Electronic structure
Ligands
Oxidation

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

これを引用

The effect of π-π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(II)-salen type complex. Comparison with the corresponding Cu(II) complex. / Oshita, Hiromi; Suzuki, Takashi; Kawashima, Kyohei; Abe, Hitoshi; Tani, Fumito; Mori, Seiji; Yajima, Tatsuo; Shimazaki, Yuichi.

:: Dalton Transactions, 巻 48, 番号 32, 01.01.2019, p. 12060-12069.

研究成果: ジャーナルへの寄稿記事

Oshita, Hiromi ; Suzuki, Takashi ; Kawashima, Kyohei ; Abe, Hitoshi ; Tani, Fumito ; Mori, Seiji ; Yajima, Tatsuo ; Shimazaki, Yuichi. / The effect of π-π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(II)-salen type complex. Comparison with the corresponding Cu(II) complex. :: Dalton Transactions. 2019 ; 巻 48, 番号 32. pp. 12060-12069.
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abstract = "In order to gain new insights into the effect of the π-π stacking interaction of the indole ring with the phenoxyl radical moiety as seen in the active form of galactose oxidase, we have prepared Ni(ii) complexes of a methoxy substituted salen-type ligand containing a pendent indole ring on the dinitrogen chelate backbone and characterized their one-electron oxidized forms. The X-ray crystal structure analysis and the other physicochemical experiments of the Ni(ii) complex revealed no significant intramolecular interaction of the indole ring with the coordination plane. On the other hand, the X-ray crystal structures of the oxidized Ni(ii) complex exhibited the π-π stacking interaction of the indole ring mainly with one of the two phenolate moieties. While the phenoxyl radical electron was delocalized on the two phenolate moieties in the Ni(ii)-salen coordination plane, the phenolate moiety in close contact with the indole moiety was considered to be the initial oxidation locus, indicating that the indole ring interacted with the phenoxyl radical by π-π stacking. The UV-vis-NIR spectrum of the oxidized Ni(ii) complex with the pendent indole ring was different from that of the complex without the side chain indole ring, but the differences were rather small in comparison with the oxidized Cu(ii)-salen complexes with the π-π stacking interaction of the indole ring. Such differences are due to the electronic structure difference, the localized radical electron on one of the phenolate moieties in the oxidized Cu(ii) complexes being more favorable for the π-π stacking interaction.",
author = "Hiromi Oshita and Takashi Suzuki and Kyohei Kawashima and Hitoshi Abe and Fumito Tani and Seiji Mori and Tatsuo Yajima and Yuichi Shimazaki",
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T1 - The effect of π-π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(II)-salen type complex. Comparison with the corresponding Cu(II) complex

AU - Oshita, Hiromi

AU - Suzuki, Takashi

AU - Kawashima, Kyohei

AU - Abe, Hitoshi

AU - Tani, Fumito

AU - Mori, Seiji

AU - Yajima, Tatsuo

AU - Shimazaki, Yuichi

PY - 2019/1/1

Y1 - 2019/1/1

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