Intramolecular triarylmethane-triarylmethylium complex: Generation, properties, and X-ray structure of a C-H bridged carbocation

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

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

A series of title carbocations was generated and isolated as stable salts. X-ray analyses revealed a preference for an unsymmetric structure in which the bridging hydrogen is localized on one of the two triarylmethane units. NMR spectroscopy showed a similar preference in solution. The bridging hydrogen fluctuates between the two chromophores in solution, and the energy barrier for the H shift is linearly correlated with the C⋯C+ separation determined by X-ray. According to an extrapolation, the energy barrier should decrease when the C⋯C+ separation is less than 2.7 Å, which suggests a new model for isolable pure organic species with a three-center-two-electron bond.

Original languageEnglish
Pages (from-to)1033-1044
Number of pages12
JournalPure and Applied Chemistry
Volume82
Issue number4
DOIs
Publication statusPublished - 2010 May 10
Externally publishedYes

Keywords

  • Carbocation
  • Hydride shift
  • Isotope effects
  • Neighboring effects
  • Three-center bond
  • Triarylmethylium
  • X-ray structure

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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