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

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4 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)4027-4034
Number of pages8
JournalACS Omega
Volume3
Issue number4
DOIs
Publication statusPublished - Jan 1 2018

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Cobalt
Carbon
Ligands
Metals
porphycene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

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.

In: ACS Omega, Vol. 3, No. 4, 01.01.2018, p. 4027-4034.

Research output: Contribution to journalArticle

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AU - Morita, Yoshitsugu

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Shimakoshi, Hisashi

AU - Hisaeda, Yoshio

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