C-H BOND ACTIVATION IN FUNCTIONALIZED ORGANIC-COMPOUNDS WITH CP-ASTERISK(PME(3))IRME(OTF) - GENERATION, STRUCTURAL CHARACTERIZATION AND METAL-BASED REARRANGEMENT OF THE ACETONE ACTIVATION PRODUCT CP-ASTERISK(PME(3))IR(ETA(3)-CH2C(OH)CH2)(+)OTF(-)

The iridium complex Cp*(PMe(3))Ir(Me)OTf (1) (Cp* = eta(5)-C-5(CH3)(5), OTf = OSO2CF3) reacts cleanly with acetone at room temperature. This reaction results in overall double C-H activation, generating the cationic eta(3)-hydroxyallyl complex Cp*(PMe(3))Ir(eta(3)-CH2C(OH)CH2)(+)OTf(-) (2), Complex 2 was characterized by X-ray diffraction and found to contain a hydrogen-bonded triflate anion. The ultimate product formed on reaction with acetone is strongly dependent upon the nature of the counterion present. Replacement of the triflate ion in 2 with other anions leads to the metallacyclobutanone Cp*(PMe(3))Ir(eta(2)-CH2COCH2), the eta(1)-enolate Cp*(PMe(3))Ir(CH2COCH3)S(p-tolyl) and the free cation salt Cp*(PMe(3))Ir(eta(3)-CH2C(OH)CH2)(+) B(3,5-C6H3(CF3)(2))(4)(-).