Intramolecular triarylmethane-triarylmethylium complexes with a naphthalene-1,8-diyl skeleton: Isolation, structure, and reactivities of the C-H-bridged carbocations

Takashi Takeda, Hidetoshi Kawai, Kenshu Fujiwara, Takanori Suzuki

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)

Abstract

Isolation and low-temperature X-ray analyses of intramolecular triarylmethane-triarylmethylium complexes with a naphthalene- 1,8-diyl-type skeleton have been achieved. These bridged cations prefer a C-H localized structure both in solution and in the solid state. The bridging hydrogen undergoes a facile intramolecular 1.5-hydride shift from one carbon to another in solution. The C-H delocalized geometry is suggested to be the transition-state structure of the degenerate rearrangement. Charge-transfer interaction from the triarylmethane to the triarylmethylium units is evident in the electronic spectra. This interaction stabilizes the present cations. Low reactivity toward Brønsted acids indicates that these species are not the reaction intermediates in the acid-assisted longbond cleavage of 1,1,2,2-tetraarylacenaphthene derivatives.

Original languageEnglish
Pages (from-to)7915-7925
Number of pages11
JournalChemistry - A European Journal
Volume13
Issue number28
DOIs
Publication statusPublished - 2007 Oct 16
Externally publishedYes

Keywords

  • Carbocations
  • Charge transfer
  • Hydride shift
  • Neighboring-group effects
  • Pen-interactions

ASJC Scopus subject areas

  • Chemistry(all)

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