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