Characterization of heterogeneous aryl-Pd(II)-oxo clusters as active species for C-H arylation.

C-H arylation with heterogeneous palladium was investigated. The surface oxidation of Pd nanoparticles with a hypervalent iodine reagent, [Ph2I]BF4, resulted in the generation of Pd(ii)-aryl-oxo clusters, which were characterized as the crucial intermediate.

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.

Rh(0)/Rh(iii) core-shell nanoparticles as heterogeneous catalysts for cyclic carbonate synthesis.

Rh(0)/Rh(iii) core-shell nanoparticles were prepared by surface oxidation of Rh nanoparticles with N-bromosuccinimide. They were employed as heterogeneous catalysts for cyclic carbonate synthesis from propylene oxide and CO2, and exhibited high activity and excellent recyclability due to Lewis acidic Rh(iii) species on the shells.