Intramolecular methylacridan-methylacridinium complexes with a phenanthrene-4,5-diyl or related skeleton: Geometry-property relationships in isolable C-H bridged carbocations

Takanori Suzuki, Yasuyo Yoshimoto, Takashi Takeda, Hidetoshi Kawai, Kenshu Fujiwara

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The isolation and low-temperature X-ray analyses of a series of intramolecular methylacridan-methylacridinium complexes have been achieved. The two chromophores are in close proximity due to an arylene spacer, such as a phenanthrene-4,5-diyl or biphenyl-2,2′-diyl unit. These bridged carbocations prefer the C-H localized structure both in solution and in the solid state. The bridging hydrogen atom undergoes a facile intramolecular hydride shift from one carbon atom to another in solution, and the energy barrier is linearly correlated with the intramolecular C⋯C+ distance in the solid-state geometry, as determined by single-crystal X-ray analyses. By extrapolation from the data, the delocalized three-center bond of [C-H-C]+ would be formed when the C⋯C+ distance is less than 2.7 Å.

Original languageEnglish
Pages (from-to)2210-2216
Number of pages7
JournalChemistry - A European Journal
Volume15
Issue number9
DOIs
Publication statusPublished - 2009 Feb 16
Externally publishedYes

Keywords

  • Carbocations
  • Hydride shift
  • Strained molecules
  • Structure elucidation
  • Three-center bonds

ASJC Scopus subject areas

  • Chemistry(all)

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