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.
| Original language | English |
|---|---|
| Pages (from-to) | 715-721 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 33 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Feb 10 2014 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Cite this
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.
In: Organometallics, Vol. 33, No. 3, 10.02.2014, p. 715-721.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Mechanism of N-h bond cleavage of aniline by a dearomatized PNP-pincer type phosphaalkene complex of Iridium(I)
AU - Chang, Yung Hung
AU - Nakajima, Yumiko
AU - Tanaka, Hiromasa
AU - Yoshizawa, Kazunari
AU - Ozawa, Fumiyuki
PY - 2014/2/10
Y1 - 2014/2/10
N2 - 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.
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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U2 - 10.1021/om401053j
DO - 10.1021/om401053j
M3 - Article
VL - 33
SP - 715
EP - 721
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 3
ER -