Directed C−H Activation and Tandem Cross‐Coupling Reactions Using Palladium Nanocatalysts with Controlled Oxidation

Controlled oxidation of palladium nanoparticles provided high‐valent PdIV oxo‐clusters which efficiently promote directed C−H halogenation reactions. In addition, palladium nanoparticles can undergo changes in oxidation states to provide both high‐valent PdIV and low‐valent Pd0 species within one system, and thus a tandem reaction of C−H halogenation and cross‐coupling (C−N, C−C, and C−S bond formation) was successfully established. Clusters: Palladium nanoparticles are selectively oxidized to generate heterogeneous PdIV oxo‐clusters, which effectively promote directed C−H halogenation. The nanoparticles can also undergo additional changes in oxidation state and thus facilitate tandem reactions involving C−H halogenation and various cross‐coupling reactions.