Highly Efficient Abnormal NHC Ruthenium Catalyst for Oppenauer-Type Oxidation and Transfer Hydrogenation Reactions

The ruthenium complex [Ru(OAc)(a-PC)2]Br (3) containing two abnormal NHC ligands is obtained by reaction of Ru(OAc)2(PPh3)2 (1) with 1-(2-diphenylphosphinoethyl)-3-mesitylimidazolium bromide in the presence of NaOAc. Complex 3 catalyzes the Oppenauer-type oxidation of a number of alcohols at unrivalled reaction rates reaching TOFs up to 550 000 h–1, at low catalyst loadings (S/C higher than 10 000) and using acetone in stoichiometric amounts. Complex 3 is also highly active in the reverse transfer hydrogenation of several ketones with 2-propanol, displaying TOFs up to 600 000 h–1.