Intramolecular rearrangement for regioselective complexation by intramolecular CH/π interaction in a hydrophobic cavity of a ruthenium coordination sphere

Takahiko Kojima, Soushi Miyazaki, Ken Ichi Hayashi, Yuichi Shimazaki, Fumito Tani, Yoshinori Naruta, Yoshihisa Matsuda

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Abstract

A RuII complex with a hydrophobic cavity formed from two 1-naphthoylamide groups was prepared. Its reactions with β-diketones gave β-diketonato complexes in which hydrophobic π-π or CH/π interactions were confirmed by NMR spectroscopy and X-ray crystallography. In the case of the asymmetric β-diketone benzoylacetone, an isomer with a CH/π interaction was afforded as the sole product owing to thermodynamic control. The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-β-diketonato coordination bonds (activation energy 52 kJ mol -1). This indicates that CH/π interactions can be more favored thermodynamically than π-π interactions in a suitable hydrophobic environment.

Original languageEnglish
Pages (from-to)6402-6410
Number of pages9
JournalChemistry - A European Journal
Volume10
Issue number24
DOIs
Publication statusPublished - Dec 3 2004

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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