Rhodium‐ and palladium‐induced B2–H activation of a derivative of the monocarba‐closo‐dodecaborate [CB11H12]– afforded two new transition metal complexes of this cluster. The products were formed in high yields under mild conditions. The complexes were fully characterized by spectroscopic methods, X‐ray crystallography, and computational analysis. The product from the reaction with rhodium was identified as a monomeric RhIII complex, while B–H activation with palladium afforded a dimeric PdII structure. Acetate‐mediated deprotonation–metalation is proposed as the mechanistic pathway.