Mechanism of N-h bond cleavage of aniline by a dearomatized PNP-pincer type phosphaalkene complex of Iridium(I)

Yung Hung Chang, Yumiko Nakajima, Hiromasa Tanaka, Kazunari Yoshizawa, Fumiyuki Ozawa

研究成果: ジャーナルへの寄稿記事

20 引用 (Scopus)

抄録

Detailed mechanistic investigations using kinetic and theoretical methods have been conducted for deprotonative N-H bond cleavage of p-YC 6H4NH2 (Y = H, MeO, Me, Cl, Br, NO2) by [K(18-crown-6)][Ir(Cl)(PPEP*)] (1a) bearing a dearomatized PNP-pincer type phosphaalkene ligand (PPEP*) to afford [Ir(NHC6H 4Y)(PPEP)] (2) with an aromatized ligand (PPEP). While 1a is in equilibrium with [K(18-crown-6)]Cl (3) and [Ir(PPEP*)] (4) in solution, the N-H bond cleavage proceeds via association of 1a with aniline, where the coordination of aniline to iridium is insignificant; instead, aniline is associated with PPEP* by hydrogen bonding. In contrast, the N-H bond cleavage of ammonia proceeds via the pentacoordinate intermediate [Ir(Cl)(NH3)(PPEP*)]. The difference between the N-H bond cleavage processes of aniline and ammonia is examined by DFT calculations.

元の言語英語
ページ(範囲)715-721
ページ数7
ジャーナルOrganometallics
33
発行部数3
DOI
出版物ステータス出版済み - 2 10 2014

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Iridium
iridium
aniline
cleavage
Ammonia
ammonia
Bearings (structural)
Ligands
ligands
Discrete Fourier transforms
Hydrogen bonds
Association reactions
Kinetics
kinetics
hydrogen
K-18 conjugate
18-crown-6

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Mechanism of N-h bond cleavage of aniline by a dearomatized PNP-pincer type phosphaalkene complex of Iridium(I). / Chang, Yung Hung; Nakajima, Yumiko; Tanaka, Hiromasa; Yoshizawa, Kazunari; Ozawa, Fumiyuki.

:: Organometallics, 巻 33, 番号 3, 10.02.2014, p. 715-721.

研究成果: ジャーナルへの寄稿記事

Chang, Yung Hung ; Nakajima, Yumiko ; Tanaka, Hiromasa ; Yoshizawa, Kazunari ; Ozawa, Fumiyuki. / Mechanism of N-h bond cleavage of aniline by a dearomatized PNP-pincer type phosphaalkene complex of Iridium(I). :: Organometallics. 2014 ; 巻 33, 番号 3. pp. 715-721.
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abstract = "Detailed mechanistic investigations using kinetic and theoretical methods have been conducted for deprotonative N-H bond cleavage of p-YC 6H4NH2 (Y = H, MeO, Me, Cl, Br, NO2) by [K(18-crown-6)][Ir(Cl)(PPEP*)] (1a) bearing a dearomatized PNP-pincer type phosphaalkene ligand (PPEP*) to afford [Ir(NHC6H 4Y)(PPEP)] (2) with an aromatized ligand (PPEP). While 1a is in equilibrium with [K(18-crown-6)]Cl (3) and [Ir(PPEP*)] (4) in solution, the N-H bond cleavage proceeds via association of 1a with aniline, where the coordination of aniline to iridium is insignificant; instead, aniline is associated with PPEP* by hydrogen bonding. In contrast, the N-H bond cleavage of ammonia proceeds via the pentacoordinate intermediate [Ir(Cl)(NH3)(PPEP*)]. The difference between the N-H bond cleavage processes of aniline and ammonia is examined by DFT calculations.",
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AB - Detailed mechanistic investigations using kinetic and theoretical methods have been conducted for deprotonative N-H bond cleavage of p-YC 6H4NH2 (Y = H, MeO, Me, Cl, Br, NO2) by [K(18-crown-6)][Ir(Cl)(PPEP*)] (1a) bearing a dearomatized PNP-pincer type phosphaalkene ligand (PPEP*) to afford [Ir(NHC6H 4Y)(PPEP)] (2) with an aromatized ligand (PPEP). While 1a is in equilibrium with [K(18-crown-6)]Cl (3) and [Ir(PPEP*)] (4) in solution, the N-H bond cleavage proceeds via association of 1a with aniline, where the coordination of aniline to iridium is insignificant; instead, aniline is associated with PPEP* by hydrogen bonding. In contrast, the N-H bond cleavage of ammonia proceeds via the pentacoordinate intermediate [Ir(Cl)(NH3)(PPEP*)]. The difference between the N-H bond cleavage processes of aniline and ammonia is examined by DFT calculations.

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