Redox-Noninnocent Behavior of Tris(2-pyridylmethyl)amine Bound to a Lewis Acidic Rh(III) Ion Induced by C-H Deprotonation

Hiroaki Kotani, Takumi Sugiyama, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Rh(III) complexes having tris(2-pyridylmethyl)amine (TPA) and its derivative as tetradentate ligands showed reversible deprotonation at a methylene moiety of the TPA ligands upon addition of a strong base as confirmed by spectroscopic measurements and X-ray crystallography. Deprotonation selectively occurred at the axial methylene moiety rather than equatorial counterparts because of the thermodynamic stability of corresponding deprotonated complexes. One-electron oxidation of the deprotonated Rh(III)-TPA complex afforded a unique TPA radical bound to the Rh(III) center by a ligand-centered oxidation. This is the first example to demonstrate emergence of the redox-noninnocent character of the TPA ligand.

Original languageEnglish
Pages (from-to)11222-11225
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number35
DOIs
Publication statusPublished - Sep 9 2015

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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