Monovalent group 15 cations L2Pn + (L = σ-donor ligands, Pn = N, P, As, Sb, Bi) have attracted significant experimental and theoretical interest because of their unusual electronic structures and growing synthetic potential. Herein, we describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis(silylene) ligand [(TBDSi2)Pn][BArF4] (TBD = 1, 8, 10, 9-triazaboradecalin; ArF= 3,5-CF3-C6H3; Pn = Sb, (2); Bi, (3)). The structures of2and3have been unambiguously characterized spectroscopically and by X-ray diffraction analysis and DFT calculations. They feature bis-coordinated Sb and Bi atoms which exhibit two lone pairs of electrons. The reactions of2and3with methyl trifluoromethane sulfonate provide a approach for the preparation of dicationic antimony(III) and bismuth(III) methyl complexes. Compounds2and3serve as 2e donors to group 6 metals (Cr, Mo), giving rise to ionic antimony and bismuth metal carbonyl complexes6–9.