Site-Specific Phenylation of Pyridine Catalyzed by Phosphido-Bridged Ruthenium Dimer Complexes:  A Prototype for C−H Arylation of Electron-Deficient Heteroarenes

Direct and selective catalytic arylation of alpha-C-H bond in pyridine with iodobenzene was achieved in up to 70% yield. Phosphido-bridged bisruthenium complexes 6a and 6b arising from Ru3(CO)12 and PPh3 were identified as active catalysts. The formation of complexes 6a and 6b was investigated, a sequence of C-H and C-P bond cleavage, cluster fragmentation, and disproportionation was established, and the intermediate ruthenium complexes lying on this pathway were isolated and fully characterized.