Visible‐Light‐Promoted Palladium‐Catalyzed Cross‐Coupling of Iodocarboranes with Disulfides and Phenylselenyl Chloride†

Comprehensive Summary This work describes a general method for the synthesis of a series of sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron‐centered carboranyl radicals. Such hypervalent boron radicals are generated by a visible‐light‐promoted Pd(0)/Pd(I) pathway. They are useful intermediates and can be trapped by disulfides and phenylselenyl chloride for the convenient construction of B—S/Se bonds.