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

研究成果: ジャーナルへの寄稿記事

9 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)11222-11225
ページ数4
ジャーナルJournal of the American Chemical Society
137
発行部数35
DOI
出版物ステータス出版済み - 9 9 2015

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Deprotonation
Oxidation-Reduction
Amines
Ligands
Ions
Oxidation
X ray crystallography
X Ray Crystallography
Thermodynamics
Thermodynamic stability
Electrons
Derivatives
tris(2-pyridylmethyl)amine

All Science Journal Classification (ASJC) codes

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

これを引用

Redox-Noninnocent Behavior of Tris(2-pyridylmethyl)amine Bound to a Lewis Acidic Rh(III) Ion Induced by C-H Deprotonation. / Kotani, Hiroaki; Sugiyama, Takumi; Ishizuka, Tomoya; Shiota, Yoshihito; Yoshizawa, Kazunari; Kojima, Takahiko.

:: Journal of the American Chemical Society, 巻 137, 番号 35, 09.09.2015, p. 11222-11225.

研究成果: ジャーナルへの寄稿記事

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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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AU - Kotani, Hiroaki

AU - Sugiyama, Takumi

AU - Ishizuka, Tomoya

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Kojima, Takahiko

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AB - 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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