Acetate Acetylacetonate Ampy Ruthenium(II) Complexes as Efficient Catalysts for Ketone Transfer Hydrogenation

The mixed acetate acetylacetonate (acac) ruthenium(II) phosphine complexes Ru(OAc)(acac)P2 [P2=(PPh3)2, Ph2P(CH2)4PPh2 (dppb)] were prepared by protonation of Ru(OAc)2(PPh3)2 with acetylacetone in dichloromethane. Reaction of the dppb derivative with 2-(aminomethyl)pyridine (ampy) affords the complex Ru(OAc)(acac)(ampy)(dppb), which converts to [Ru(acac)(ampy)(dppb)](OAc) in toluene at 90 °C. In the former derivative the ampy ligand is monodentate and coordinates through the NH2-moiety. The isolated acac complexes are active catalysts for the transfer hydrogenation of ketones with loadings as low as 0.01 mol%, the ampy having a strong accelerating effect. Several aromatic and aliphatic ketone substrates are converted to their corresponding alcohols, and different electronic influences through substituents on acetophenone are tolerated