Synthesis and crystal structures of novel tertiary butyl substituted (pseudo-)halogen bismuthanes

Herein we present the synthesis and characterization of di-tertiary butyl substituted (pseudo-)halogen bismuthanes tBu(2)BiX (X = Cl (1), Br (2), I (3), CN (4), N-3 (5), SCN (6)). These compounds were obtained via different reaction paths. Compound 1 was obtained by a Grignard reaction of BiCl3 with two equivalents of tBuMgCl, whereas compounds 2, 3, 4 and 6 were synthesised by a oxidative addition/reductive elimination pathway starting from tBu(3)Bi and X-2 (X = Br, I, CN, SCN). Finally, azide 5 was obtained by the reaction of 1 and NaN3. Secondary bonding interactions in the solid state within all the investigated compounds (1-6) cause additional stabilisation. Starting from tBu(2)BiCl, the completely tbutyl substituted ternary interpnictogen compound tBu(2)Bi(tBuP)SbtBu(2) (7) was synthesized through the reaction with [tBu(2)SbP(tBu)Li(Et2O)](2). All new compounds were characterized by means of X-ray diffraction and mass spectrometry as well as NMR and IR spectroscopy.