Catalytic C-H amination driven by intramolecular ligand-to-nitrene one-electron transfer through a rhodium(III) centre

Daiki Fujita, Hideki Sugimoto, Yoshihito Shiota, Yuma Morimoto, Kazunari Yoshizawa, Shinobu Itoh

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Werner type six-coordinate rhodium(iii) complexes coordinated by a planar trianionic ligand and two axial aniline ligands are synthesised. The trianionic ligand behaves as a redox-active ligand to form a ligand radical species upon one-electron oxidation of the complex. The rhodium(iii) complexes catalyse C-H amination of external substrates such as xanthene with tosylazide as the nitrene source. DFT-calculation and kinetic deuterium isotope effects indicate that a di-radical rhodium(iii) complex formed by one-electron transfer from the redox-active ligand to the nitrene group works as a reactive intermediate to induce aliphatic C-H activation.

Original languageEnglish
Pages (from-to)4849-4852
Number of pages4
JournalChemical Communications
Volume53
Issue number35
DOIs
Publication statusPublished - 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Chemistry(all)
  • Surfaces, Coatings and Films
  • Metals and Alloys
  • Materials Chemistry

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