Selective B(3)‐H activation without auxiliary reagents affording multinuclear Ir(III) complexes with (o‐carboranyl)dithioester ligands

A method was developed to link two or three o‐carborane moieties to form a series of carboranyl dithioester bridging ligands via in situ substitution of haloalkanes by tetraphenylphosphonium carboranyldithiocarboxylates. Based on these ligands, direct B‐H activation without the assistance of Ag(I) and alkali was successfully achieved with half‐sandwich Ir(III) substrate [Cp*IrCl2]2 to yield corresponding bimetallic or trimetallic complexes. Single crystal structure analyses of the B‐H activated complexes and corresponding SnCl2‐inserted derivatives confirm the selective B(3)‐H activation in these complexes.