Ultralong carbon-carbon bonds in dispirobis(10-methylacridan) derivatives with an acenaphthene, pyracene, or dihydropyracylene skeleton

Hidetoshi Kawai, Takashi Takeda, Kenshu Fujiwara, Makoto Wakeshima, Yukio Hinatsu, Takanori Suzuki

Research output: Contribution to journalArticlepeer-review

54 Citations (Scopus)

Abstract

Acenapthalene, pyracene, and dihydropyracylene attached to two units of spiroacridan are a novel class of hexaphenylethane (HPE) derivatives that have an ultralong Csp3-Csp3 bond (1.77-1.70 Å). These sterically challenged molecules were cleanly prepared by C-C bond formation through two-electron reduction from the less-hindered dications. These ultralong bonds were realized based on several molecular-design concepts including enhanced "front strain" through "multiclamping" by means of fusing or bridging aryl groups in the HPE molecule. The lengths of these ultralong bonds and their relation to the conformation (torsional angle) were also validated by means of theoretical calculations. Bond-fission experiments revealed that the bonds are more easily cleaved than standard covalent bonds to produce the corresponding dication upon oxidation with an increase in the length of the C-C bond.

Original languageEnglish
Pages (from-to)5780-5793
Number of pages14
JournalChemistry - A European Journal
Volume14
Issue number19
DOIs
Publication statusPublished - 2008 Jun 27
Externally publishedYes

Keywords

  • Crystallography
  • Long bonds
  • Redox chemistry
  • Strained molecules
  • Through-bond interactions

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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