CH bond activation in aromatic ketones mediated by iridium-tris(pyrazolyl)borate complexes.

Reaction of complex [Tp Me2 Ir(η 4 -CH 2 C(Me)C(Me)C 2 )] (1) with a series of aromatic ketones at 130 °C renders, by means of a selective ortho -CH activation, Ir(III)-metallacycles 2-5, which display an Ir-H bond. When [Tp Me2 Ir(C 6 H 5 ) 2 N 2 ] (6) is treated with 2-(trifluoromethyl)acetophenone and 2-fluoroacetophenone at 80 °C, the formation of dimeric (7) and trimeric architectures (8) is achieved through the meta - and para -CH activation of the aromatic ketone, respectively. The generation of complexes 2-5 is proposed to occur by the initial formation of Ir(III) η 1 -ketone adducts as key intermediates, followed by aromatic CH activations and the release of a butadiene ligand. The formation of complexes 7 and 8 involves an assisted process in which a metal center activation of the less sterically hindered C-H bond of the aromatic ketone takes place (releasing a benzene molecule), followed by the coordination of the carbonyl group, which generates the respective dimeric and trimeric structures. Complexes 7 and 8 are efficient catalysts for the transfer hydrogenation of ketones and aldehydes using isopropanol as the hydrogen source. All complexes have been fully characterized by NMR spectroscopy, FT-IR, elemental analysis and, in the cases of 7 and 8, X-ray crystallography. Details of the reaction conditions, isolation of the products, and proposals for the pathways of formation of complexes 2-5 and 7-8 are discussed.