Evidence for the Net Addition of Arene C−H Bonds across a Ru(II)−Hydroxide Bond

TpRu(PMe3)2(OH) (1) reacts with C6D6 to initiate H/D exchange between the hydroxide ligand and the deuterated benzene. In addition, complex 1 catalyzes H/D exchange between H2O and C6D6. Mechanistic and computational studies suggest that a likely reaction pathway for the H/D exchange involves loss of PMe3 to produce {TpRu(PMe3)(OH)}, followed by the net addition of a benzene C−H(D) bond across the Ru−OH bond to form the putative complex TpRu(PMe3)(OH2)(Ph).