Abstract
Iridium complexes containing a triazolylidene ligand with an appended methylpyridinium site undergo either aromatic C(sp 2)−H bond activation or exocyclic C(sp 3)−H bond activation of the N-bound methyl group. The selectivity of these bond activations is controlled by the remote substituent R of the triazolylidene ligand. Iterative computational and synthetic experiments provide evidence for more facile C(sp 2)−H bond activation for a variety of remote substituents with R = Me, CH 2 C 6 F 5 , CH 2 CH 2 C 6 H 5. For triazolylidene ligands with a benzylic substituent, C(sp 2