Binary interpnictogen compounds bearing diaryl bismuth fragments bound to all tighter pnictogens

Multiple interpnictogen compounds with covalent single bonds between a diarylbismuth fragment and all lighter pnictogens were prepared from the corresponding diarylhalido bismuthanes. The aminobismuthanes Ph2BiNMe2 (1) and Mes(2)BiNMe(2) (2) (Mes = 2,4,6-trimethylphenyl-) have been obtained via a salt metathesis reaction and compound 2 was successfully reacted with tBuNH(2) in a condensation reaction to yield Mes(2)BiNHtBu (3). The bismuthanyl phosphanes Ar2BiPtBu2 (Ar = Ph: 4 and Ar = Mes: 5) and arsanes ArAiAstBup (Ar = Ph: 8 and Ar = Mes: 9) were also obtained via salt metathesis. Through a tri-methylsilyl halide abstraction reaction of the diary( halido bismuthanes and EtBu(SiMe3)(2) (E = P and As), the bismuthanyl phosphanes Ar2BiPtBu(SiMe3) (Ar = Ph: 6; Ar = Mes: 7) and the arsanes Ar(2)BiAstBu(SiMe3) (Ar = Ph: 10; Ar = Mes: 11) have been prepared. Bismuthanyl stibanes were accessed via a condensation reaction of Mes(2)SbH with 1 or 2, respectively. The compound Ph(7)BiSbMes(2) (12), which has different substituents at the bismuth and antimony atoms, was isolated and fully characterised. In contrast, the isolation of Mes(2)BiSbMes 2 (13) was not possible due to a dynamic equilibrium with Mes(4)Bi(2) and Mes(4)Sb(2) which was investigated via low-temperature H-1-NMR spectroscopy in solution. The isolated compounds with a single bond between bismuth and the heavy pnictogens arsenic and antimony are rare examples of their kind. All isolated compounds (1-12) were characterised by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction.

Automated summary

Multiple interpnictogen compounds with covalent single bonds between a diarylbismuth fragment and lighter pnictogens were synthesized. The compounds were characterized using NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray diffraction.