2,6‐Diisopropylphenyl‐Substituted Bismuth Compounds: Synthesis, Structure, and Reactivity

The 2,6‐di iso propylphenyl (Dipp) substituent is introduced to diaryl bismuth chemistry. Dipp 2 BiBr ( 1‐Br ) was prepared by a Grignard reaction and subsequently used as precursor for synthesis of the other diaryl halido bismuthanes Dipp 2 BiX ( 1‐X , X=F, Cl, I) and the corresponding triflate Dipp 2 BiOTf ( 1‐OTf ). Moreover, 1,1,2,2‐tetrakis(2,6‐di iso propylphenyl)dibismuthane ( 2 ) was prepared. All isolated compounds were characterized via single crystal X‐ray diffraction analysis, NMR spectroscopy, IR spectroscopy, and elemental analysis. Furthermore, the reactivity of a dibismuthane towards elemental sulfur was investigated, and the formed dibismuthanyl tri‐ and pentasulfide ( 3   a , 3   b ) were characterized by single crystal X‐ray analysis. Functionalization of the diaryl halido bismuthanes with LiP t Bu 2 or t Bu 2 PTMS (TMS=SiMe 3 ) gives access to the interpnictogen compound Dipp 2 Bi−P t Bu 2 ( 4 ), which shows a rare example of a covalent Bi−P bond.