Cobalt-Carbon Bond Formation Reaction via Ligand Reduction of Porphycene-Cobalt(II) Complex and Its Noninnocent Reactivity

Taro Koide, Isao Aritome, Tatsuya Saeki, Yoshitsugu Morita, Yoshihito Shiota, Kazunari Yoshizawa, Hisashi Shimakoshi, Yoshio Hisaeda

研究成果: ジャーナルへの寄稿記事

5 引用 (Scopus)

抄録

The interesting redox properties and reactivity of metalloporphycene have been studied for decades; however, the detailed experimental investigation on the reactivity and reaction mechanism under inert condition combined with theoretical calculations had not been performed so far. In this study, the novel reactivity of the reduced form of the cobalt porphycene with alkyl halides to form cobalt-carbon (Co-C) bonds was revealed. Under electrochemical reductive conditions, not the central cobalt, but the ligand was reduced and reacted with alkyl halides to afford the cobalt-alkyl complexes under N2 atmosphere in a glovebox. The reaction mechanism was clarified by the combination of experimental and theoretical studies that the porphycene ligand works as a noninnocent ligand and allows the SN2-type Co-C bond formation. This result provides us the possibility of the reaction triggered by the reduction of ligand with macrocyclic π-conjugated system, not by the reduction of metal.

元の言語英語
ページ(範囲)4027-4034
ページ数8
ジャーナルACS Omega
3
発行部数4
DOI
出版物ステータス出版済み - 1 1 2018

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Cobalt
Carbon
Ligands
Metals
porphycene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

これを引用

Cobalt-Carbon Bond Formation Reaction via Ligand Reduction of Porphycene-Cobalt(II) Complex and Its Noninnocent Reactivity. / Koide, Taro; Aritome, Isao; Saeki, Tatsuya; Morita, Yoshitsugu; Shiota, Yoshihito; Yoshizawa, Kazunari; Shimakoshi, Hisashi; Hisaeda, Yoshio.

:: ACS Omega, 巻 3, 番号 4, 01.01.2018, p. 4027-4034.

研究成果: ジャーナルへの寄稿記事

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abstract = "The interesting redox properties and reactivity of metalloporphycene have been studied for decades; however, the detailed experimental investigation on the reactivity and reaction mechanism under inert condition combined with theoretical calculations had not been performed so far. In this study, the novel reactivity of the reduced form of the cobalt porphycene with alkyl halides to form cobalt-carbon (Co-C) bonds was revealed. Under electrochemical reductive conditions, not the central cobalt, but the ligand was reduced and reacted with alkyl halides to afford the cobalt-alkyl complexes under N2 atmosphere in a glovebox. The reaction mechanism was clarified by the combination of experimental and theoretical studies that the porphycene ligand works as a noninnocent ligand and allows the SN2-type Co-C bond formation. This result provides us the possibility of the reaction triggered by the reduction of ligand with macrocyclic π-conjugated system, not by the reduction of metal.",
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AU - Koide, Taro

AU - Aritome, Isao

AU - Saeki, Tatsuya

AU - Morita, Yoshitsugu

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Shimakoshi, Hisashi

AU - Hisaeda, Yoshio

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N2 - The interesting redox properties and reactivity of metalloporphycene have been studied for decades; however, the detailed experimental investigation on the reactivity and reaction mechanism under inert condition combined with theoretical calculations had not been performed so far. In this study, the novel reactivity of the reduced form of the cobalt porphycene with alkyl halides to form cobalt-carbon (Co-C) bonds was revealed. Under electrochemical reductive conditions, not the central cobalt, but the ligand was reduced and reacted with alkyl halides to afford the cobalt-alkyl complexes under N2 atmosphere in a glovebox. The reaction mechanism was clarified by the combination of experimental and theoretical studies that the porphycene ligand works as a noninnocent ligand and allows the SN2-type Co-C bond formation. This result provides us the possibility of the reaction triggered by the reduction of ligand with macrocyclic π-conjugated system, not by the reduction of metal.

AB - The interesting redox properties and reactivity of metalloporphycene have been studied for decades; however, the detailed experimental investigation on the reactivity and reaction mechanism under inert condition combined with theoretical calculations had not been performed so far. In this study, the novel reactivity of the reduced form of the cobalt porphycene with alkyl halides to form cobalt-carbon (Co-C) bonds was revealed. Under electrochemical reductive conditions, not the central cobalt, but the ligand was reduced and reacted with alkyl halides to afford the cobalt-alkyl complexes under N2 atmosphere in a glovebox. The reaction mechanism was clarified by the combination of experimental and theoretical studies that the porphycene ligand works as a noninnocent ligand and allows the SN2-type Co-C bond formation. This result provides us the possibility of the reaction triggered by the reduction of ligand with macrocyclic π-conjugated system, not by the reduction of metal.

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