Selective B–H Bond Activation of Carboranylthioamide Ligands and their Ability to Form a Metallacycle

Herein, the reactivities of different carboranylthioamide ligands with Rh/Ir half‐sandwich precursors were explored. The results revealed that Rh activated the B(3)H bond in the o ‐carboranylthioamide ligand, forming a dinuclear metallacycle. However, when the N atom's site was changed in the pyridine group, deboronization occurred. Additionally, when more stable m ‐ and p ‐carboranylthioamide ligands were used, a linkerless tetranuclear metallacycle possessing an activated B(2)H bond was formed, revealing the capability of the rigid carborane skeleton to precisely control the metallacycle topology and providing a universal paradigm for designing ligand space programing in supramolecular assembly.