The weakly coordinating [B<sub>12</sub>Cl<sub>12</sub>]<sup>2-</sup> originates from a family of
carboranes typically reserved for application in coordination chemistry. Here,
we show its readily accessible Ag(I) salt, [Ag]<sub>2</sub>[B<sub>12</sub>Cl<sub>12</sub>],
can be used as a catalyst in the PhICl<sub>2</sub> mediated chlorination of
arenes, alkenes, and alkynes. The promising activity displayed by [Ag]<sub>2</sub>[B<sub>12</sub>Cl<sub>12</sub>]
over a variety of commercially available Ag(I) sources merits its incorporation
to the toolkit of commonly screened silver catalysts in synthesis.