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

Abstract

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 Mes₂BiNMe₂ (2) (Mes = 2,4,6-trimethylphenyl-) have been obtained via a salt metathesis reaction and compound 2 was successfully reacted with tBuNH₂ in a condensation reaction to yield Mes₂BiNHtBu (3). The bismuthanyl phosphanes Ar₂BiPtBu₂ (Ar = Ph: 4 and Ar = Mes: 5) and arsanes Ar₂BiAstBu₂ (Ar = Ph: 8 and Ar = Mes: 9) were also obtained via salt metathesis. Through a trimethylsilyl halide abstraction reaction of the diaryl halido bismuthanes and EtBu(SiMe₃)₂ (E = P and As), the bismuthanyl phosphanes Ar₂BiPtBu(SiMe₃) (Ar = Ph: 6; Ar = Mes: 7) and the arsanes Ar₂BiAstBu(SiMe₃) (Ar = Ph: 10; Ar = Mes: 11) have been prepared. Bismuthanyl stibanes were accessed via a condensation reaction of Mes₂SbH with 1 or 2, respectively. The compound Ph₂BiSbMes₂ (12), which has different substituents at the bismuth and antimony atoms, was isolated and fully characterised. In contrast, the isolation of Mes₂BiSbMes₂ (13) was not possible due to a dynamic equilibrium with Mes₄Bi₂ and Mes₄Sb₂ which was investigated via low-temperature ¹H-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.