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

Monovalent group 15 cations L(2)Pn + (L = sigma-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][BAr4F] (TBD = 1, 8, 10, 9-triazaboradecalin; Ar-F = 3,5-CF3-C6H3; 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. Tetrylones show unique electronic properties and display potantial as soluble molecular allotropes, but until now, the chemistry of Tetrylone homologs remains underexplored. Here, the authors describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis silylene ligand and explore their reactivity.

Automated summary

In this study, a series of antimony(I) and bismuth(I) cations supported by a bis(silylene) ligand were synthesized and characterized. These compounds exhibited bis-coordinated antimony and bismuth atoms with two lone pairs of electrons. They can undergo reactions with methyl trifluoromethane sulfonate to form dicationic antimony(III) and bismuth(III) methyl complexes. Additionally, compounds 2 and 3 can act as 2e donors to group 6 metals, resulting in the formation of ionic antimony and bismuth metal carbonyl complexes.