Aerobic oxidation with bifunctional molecular catalysts

A new series of half-sandwich group 8 and 9 metal complexes bearing a metal/NH bifunctional moiety were synthesized from benzylic amines. The isolable Ir amide complexes serve as effective catalysts for aerobic oxidative transformation of secondary and primary alcohols into the corresponding ketones and esters under mild conditions. The aerobic oxidative kinetic resolution of racemic secondary alcohols with chiral bifunctional Ir catalysts was found to proceed smoothly under mild conditions with high selectivity. A novel imido-bridged dirhodium complex, which may be regarded as a dinuclear variant of the bifunctional mononuclear amide complexes, also proved to promote aerobic oxidation of a secondary alcohol and H(2).