title: Redox-Noninnocent Behavior of Tris(2-pyridylmethyl)amine Bound to a Lewis Acidic Rh(III) Ion Induced by C-H Deprotonation.
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.
authors: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba , 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan.
authors: Hiroaki
authors: H
authors: Kotani
authors: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba , 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan.
authors: Takumi
authors: T
authors: Sugiyama
authors: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba , 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan.
authors: Tomoya
authors: T
authors: Ishizuka
authors: Institute for Materials Chemistry and Engineering, Kyushu University , Motooka, Nishi-Ku, Fukuoka 819-0395, Japan.
authors: Yoshihito
authors: Y
authors: Shiota
authors: 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.
authors: Kazunari
authors: K
authors: Yoshizawa
authors: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba , 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan.
authors: Takahiko
authors: T
authors: Kojima
mesh_terms: D002244:Carbon / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011522:Protons; D011725:Pyridines / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D058116:Lewis Acids; D009942:Organometallic Compounds; D011522:Protons; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; D002244:Carbon; D012238:Rhodium