Doubly N-Fused [24]Pentaphyrin Silicon Complex and Its Fluorosilicate: Enhanced Möbius Aromaticity in the Fluorosilicate

Shin Ichiro Ishida, Jun Oh Kim, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Treatment of nonaromatic N-fused [24]pentaphyrin with trichloromethylsilane in the presence of a base afforded doubly N-fused [24]pentaphyrin and its silicon complex. Addition of fluoride ion to the silicon complex led to the formation of its fluorosilicate as an unprecedented monoanionic six-coordinated SiIVcomplex of porphyrinoid. Treatment of the fluorosilicate with acid led to the recovery of the silicon complex. The doubly N-fused pentaphyrin, the silicon complex, and the fluorosilicate were all characterized as distinct Möbius aromatic molecules by spectroscopic measurements and X-ray crystallographic analyses. Importantly, the second N-fusion reaction, Si-incorporation and fluoride addition to the Si-atom enhanced the aromaticity of doubly N-fused [24]pentaphyrins in this order. Tamao–Fleming oxidation of the silicon complex gave β-keto doubly N-fused pentaphyrin and triply fused [24]pentaphyrin, which were nonaromatic and Hückel anti-aromatic, respectively.

Original languageEnglish
Pages (from-to)16554-16561
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number46
DOIs
Publication statusPublished - 2016 Nov 7

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Silicon
Fluorides
Fusion reactions
Ions
Recovery
X rays
Atoms
Oxidation
Molecules
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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abstract = "Treatment of nonaromatic N-fused [24]pentaphyrin with trichloromethylsilane in the presence of a base afforded doubly N-fused [24]pentaphyrin and its silicon complex. Addition of fluoride ion to the silicon complex led to the formation of its fluorosilicate as an unprecedented monoanionic six-coordinated SiIVcomplex of porphyrinoid. Treatment of the fluorosilicate with acid led to the recovery of the silicon complex. The doubly N-fused pentaphyrin, the silicon complex, and the fluorosilicate were all characterized as distinct M{\"o}bius aromatic molecules by spectroscopic measurements and X-ray crystallographic analyses. Importantly, the second N-fusion reaction, Si-incorporation and fluoride addition to the Si-atom enhanced the aromaticity of doubly N-fused [24]pentaphyrins in this order. Tamao–Fleming oxidation of the silicon complex gave β-keto doubly N-fused pentaphyrin and triply fused [24]pentaphyrin, which were nonaromatic and H{\"u}ckel anti-aromatic, respectively.",
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Doubly N-Fused [24]Pentaphyrin Silicon Complex and Its Fluorosilicate : Enhanced Möbius Aromaticity in the Fluorosilicate. / Ishida, Shin Ichiro; Kim, Jun Oh; Kim, Dongho; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 22, No. 46, 07.11.2016, p. 16554-16561.

Research output: Contribution to journalArticle

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