title: Experimental and computational studies on the iridium activation of aliphatic and aromatic C-H bonds of alkyl aryl ethers and related molecules.
abstract: Reaction of the Ir(III) complex [(Tp(Me2))Ir(C(6)H(5))(2)(N(2))] (1N(2)) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp(3))-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(Tp(Me2))Ir(H){=C(H)C(6)H(4)-o-O}] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already reported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(Tp(Me2))Ir(H){=C(H)OC(6)H(4)-o-}] (B), anisole can react with 1 with cleavage of the O-CH(3) bond and formation of a new carbon-carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1N(2) and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken.
authors: Instituto de Investigaciones Químicas and Departamento de Química Inorgánica, Consejo Superior de Investigaciones Científicas and Universidad de Sevilla, Av. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain.
authors: Patricia
authors: P
authors: Lara
authors: Margarita
authors: M
authors: Paneque
authors: Manuel L
authors: ML
authors: Poveda
authors: Laura L
authors: LL
authors: Santos
authors: José E V
authors: JE
authors: Valpuesta
authors: Ernesto
authors: E
authors: Carmona
authors: Salvador
authors: S
authors: Moncho
authors: Gregori
authors: G
authors: Ujaque
authors: Agustí
authors: A
authors: Lledós
authors: Eleuterio
authors: E
authors: Alvarez
authors: Kurt
authors: K
authors: Mereiter