Iridium‐Induced Regioselective B−H and C−C Activations at Azo‐Substituted o ‐Carboranes

p ‐Methoxybenzeneazo‐substituted o ‐carboranes have been synthesized and their reactivity with half‐sandwich iridium and rhodium complexes has been investigated in detail. A variety of solvent‐ and base‐dependent, highly site‐selective B−H and C−C σ‐bond activations at the C/B cage have been observed. While the use of CH 3 OH leads to the formation of metallacarboranes, o ‐carborane clusters undergo cyclometallation reactions involving B(6)−H, B(4)−H or a rare B(7)−H activation in CH 2 Cl 2 . The synthesis of a unique pseudo‐ closo ‐iridacarborane through a very unconventional metal‐mediated C cage −C cage activation is described in this contribution.