Stable Radical Cation and Dication of an N-Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity

One- and two-electron oxidation of a digallene stabilized by an N-heterocyclic carbene afforded the first stable gallium-based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of pi electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu(3)SnH and cyclo-S-8 was studied; a digallium-hydride cation salt containing a Ga-Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder-like Ga4S4 core structure were obtained, respectively.