Neutral Pd(X)(eta(3)-allyl) (X = Cl, OAc (acetate)) complexes bearing mono-coordinating NHC ligands have been synthesized, characterized and employed to catalyze the aerobic oxidation of unprotected 1,2- and 1,3-diols selectively to hydroxy ketones. A comparison of the catalytic performance of these precursors with a reference system has shown that the precursor with the ligands N,N'-bis(adamantyl)imidazol-2-ylidene and chloride is the most efficient for the chemoselective oxidation of 1,2-diols is concerned. High-pressure H-1 NMR (HPNMR) experiments in combination with catalytic batch reactions have provided valuable information on the activation of the precursor as well as on the stability of the catalysts. (C) 2010 Elsevier B.V. All rights reserved.