Transition-Metal Oxos as the Lewis Basic Component of Frustrated Lewis Pairs.

The reaction of oxorhenium complexes that incorporate diamidopyridine (DAP) ligands with B(C6F5)3 results in the formation of classical Lewis acid-base adducts. The adducts effectively catalyze the hydrogenation of a variety of unactivated olefins at 100 °C. Control reactions with these complexes or B(C6F5)3 alone did not yield any hydrogenated products under these conditions. Mechanistic studies suggest a frustrated Lewis pair is generated between the oxorhenium DAP complexes and B(C6F5)3, which is effective at olefin hydrogenation. Thus, we demonstrate for the first time that the incorporation of a transition-metal oxo in a frustrated Lewis pair can have a synergistic effect and results in enhanced catalytic activity.