Cesium carbonate mediated C–H functionalization of perhalogenated 12-vertex carborane anions

C–H functionalization of undecahalogenated carborane anions, [HCB₁₁X₁₁⁻] (X = Cl, Br, I), is performed with Cs₂CO₃ in acetonitrile. We show that the requisite Cl, Br and I carborane dianions can all be efficiently accessed with Cs₂CO₃. The utilization of Cs₂CO₃ eliminates the complications associated with competing E2 elimination reactions providing an efficient, more functional group tolerant, and broader scope than previously reported. The ensuing functionalized cages provide potential synthons for constructing advanced materials and other molecular architectures for various applications.