Xiaohai Wang, Meitian Fu, Xuran Pan, Jiaxin Xi, Zheng Wang, Xinyao Li, Shimeng Li
The construction of stable B-As and B-Sb bonds has long been a formidable challenge. Herein, we present a mild visible-light-promoted nickel-catalyzed radical cross-coupling strategy that directly forges B-As and B-Sb bonds on carborane cages. This protocol efficiently converts iodocarboranes and triarylarsanes/stibanes into a series of previously inaccessible, well-characterized boron-arsanylated and boron-stibanylated carboranes at room temperature. The unique carborane framework stabilizes these typically labile bonds, yielding air- and thermally stable compounds, as confirmed by X-ray crystallography. This work provides a general radical-based platform for exploring boron-heavier pnictogen chemistry.