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 |
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Pages (from-to) | 715-721 |
Number of pages | 7 |
Journal | Organometallics |
Volume | 33 |
Issue number | 3 |
DOIs | |
Publication status | Published - Feb 10 2014 |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry