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

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• 作者：Hiroaki Kotani ; Takumi Sugiyama ; Tomoya Ishizuka ; Yoshihito Shiota ; Kazunari Yoshizawa ; Takahiko Kojima
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 9, 2015
• 年：2015
• 卷：137
• 期：35
• 页码：11222-11225
• 全文大小：307K
• ISSN：1520-5126

文摘

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)鈥揟PA 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.