Addition of S‐Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano‐Bridged Derivatives

The reactions of novel S‐heterocyclic carbenes (SHCs), which were prepared by the cycloaddition of disilenes and digermenes to CS₂, with C₆₀ and Sc₃N@I_h‐C₈₀ afforded the corresponding methano‐bridged fullerenes. The [6,6]‐closed and [6,6]‐open structures were characterized for the SHC adducts of C₆₀ and Sc₃N@I_h‐C₈₀, respectively. These derivatives exhibited relatively low oxidation potentials, indicative of the electron‐donating effects of the SHC addends. The electronic properties of the SHC derivatives were clarified by the density functional theory calculations.