AbstractReaction of the IrIII complex [(TpMe2)Ir(C6H5)2(N2)] (1⋅N2) with ortho‐cresol (2‐methylphenol) occurs with cleavage of the OH and two C(sp3)H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(TpMe2)Ir(H){C(H)C6H4‐o‐O}] (2). The analogous reaction of 2‐ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already reported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom‐stabilized hydride carbene [(TpMe2)Ir(H){C(H)OC6H4‐ o‐}] (B), anisole can react with 1 with cleavage of the OCH3 bond and formation of a new carbon–carbon bond. In contrast, only CH bond‐activation products with structures akin to B result from 1⋅N2 and 3,5‐dimethylanisole (complex 8) or 4‐fluoroanisole (9). Using anisole as a model, a computational study of the triple CH bond activation (two aliphatic CH bonds plus an ortho‐metalation reaction) that is responsible for the formation of these heteroatom‐stabilized hydride carbenes has been undertaken.