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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 , and
- Takahiko Kojima
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† Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan
‡ Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka 819-0395, Japan
§ Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, Nishikyo-ku, Kyoto 615-8520, Japan
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.
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