Stable heavy main group element radicals are challenging synthetic targets. Although several strategies have been developed to stabilize such odd-electron species, the number of heavier pnictogen-centered radicals is limited. We report on a series of two-coordinated pnictogen-centered radical cations [(cAAC)EGa(Cl)L][B(CF)] (cAAC = [HC(CMe)NDipp]C; Dipp = 2,6--PrCH; E = As , Sb , Bi ; L = HC[C(Me)NDipp]) synthesized by one-electron oxidation of L(Cl)Ga-substituted pnictinidenes (cAAC)EGa(Cl)L (E = As , Sb , Bi ). - were characterized by electron paramagnetic resonance (EPR) spectroscopy and single crystal X-ray diffraction (sc-XRD) (, ), while quantum chemical calculations support their description as carbene-coordinated pnictogen-centered radical cations. The low thermal stability of enables access to metalloid bismuth clusters as shown by formation of [{LGa(Cl)}Bi][B(CF)] ().
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