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

Research output: Contribution to journalArticle

20 Citations (Scopus)

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 languageEnglish
Pages (from-to)715-721
Number of pages7
JournalOrganometallics
Volume33
Issue number3
DOIs
Publication statusPublished - Feb 10 2014

Fingerprint

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

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 journalArticle

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). In: Organometallics. 2014 ; Vol. 33, No. 3. pp. 715-721.
@article{f5492a5574934ebeb0279d541ce7214a,
title = "Mechanism of N-h bond cleavage of aniline by a dearomatized PNP-pincer type phosphaalkene complex of Iridium(I)",
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.",
author = "Chang, {Yung Hung} and Yumiko Nakajima and Hiromasa Tanaka and Kazunari Yoshizawa and Fumiyuki Ozawa",
year = "2014",
month = "2",
day = "10",
doi = "10.1021/om401053j",
language = "English",
volume = "33",
pages = "715--721",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "3",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=84893850193&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84893850193&partnerID=8YFLogxK

U2 - 10.1021/om401053j

DO - 10.1021/om401053j

M3 - Article

AN - SCOPUS:84893850193

VL - 33

SP - 715

EP - 721

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 3

ER -