Thermal reactions of Ru3(CO)12 with two equivalents of N,O-bidentate ligands L1H-L7H (naphthyl-substituted Schiff-bases) afforded the corresponding Ru(II) carbonyl complexes [L2Ru(CO)2] 1a-1g in good yields. All the Ru complexes were well characterized by elemental analysis, FT-IR, NMR and HR-MS. The molecular structures of 1c, 1e and 1g were reconfirmed by X-ray crystallography. These complexes showed high activity in the selective oxidation of benzylic C-H bonds with tert-butylhydroperoxide (TBHP) under mild conditions to give aryl ketones in 60 %–98 % yields. This catalytic protocol proceeds at room temperature with low catalyst loading (1.0 mol%), displays broad functional-group compatibility and has potential application for industry-scale reactions.