Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 37221189.
- Also identified by DOI 10.1038/s41467-023-38606-2 and PMC identifier 10206093.
- Licence recorded as CC BY.
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Abstract
Monovalent group 15 cations L<sub>2</sub>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<sub>2</sub>)Pn][BAr<sup>F</sup><sub>4</sub>] (TBD = 1, 8, 10, 9-triazaboradecalin; Ar<sup>F</sup> = 3,5-CF<sub>3</sub>-C<sub>6</sub>H<sub>3</sub>; 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.