Highly Active and Robust Ruthenium Complexes Based on Hemilability of Hybrid Ligands for C–H Oxidation

Evaluation of the hemilability of hybrid ligands provides a key to understand the metal–ligand cooperation in transition metal catalysis. Here, we design and synthesize a type of Ru^II complexes based on the hemilability of N-heterocyclic carbenes (NHCs), pyridine, and pyrazole, to compare their activity with other reported Ru catalysts in benzylic C–H oxidation. The Ru^II catalysts showed ultrastrong catalytic activity in water at room temperature and achieved a turnover frequency (TOF) of 114 h^–1, which is the highest TOF value ever reported for Ru-catalyzed benzylic C–H oxidation. The addition of tridentate hybrid ligands in the Ru central position has two beneficial effects: NHCs with a stronger donor ability stabilize the Ru center; however, nitrogen ligands with a relatively weaker donor ability release from the Ru center, so that they induce a reaction. UV–vis, high-resolution electrospray ionization mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR) spectrometry, the trapping of radicals, and the density functional theory calculations (DFT) suggested that a cation catalyst L–Ru^II–^tBuO₂H is formed via the reaction between starting RuII catalysts and tert-butyl hydroperoxide, which further undergoes a cleavage of the O–O bond to generate a radical and a cation L–Ru^III–OH active intermediate.