Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations

Monovalent group 15 cations L 2 Pn + (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 [(TBDSi 2 )Pn][BAr F 4 ] (TBD = 1, 8, 10, 9-triazaboradecalin; Ar F = 3,5-CF 3 -C 6 H 3 ; Pn = Sb, ( 2 ); Bi, ( 3 )). The structures of 2 and 3 have 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 of 2 and 3 with methyl trifluoromethane sulfonate provide a approach for the preparation of dicationic antimony(III) and bismuth(III) methyl complexes. Compounds 2 and 3 serve as 2e donors to group 6 metals (Cr, Mo), giving rise to ionic antimony and bismuth metal carbonyl complexes 6–9 .