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

The 2,6-diisopropylphenyl (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-diisopropylphenyl)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 LiPtBu2 or tBu(2)PTMS (TMS=SiMe3) gives access to the interpnictogen compound Dipp(2)Bi-PtBu2 (4), which shows a rare example of a covalent Bi-P bond.

Automated summary

Introduction of the 2,6-diisopropylphenyl (Dipp) substituent led to the synthesis of various diaryl bismuth compounds, which were characterized for their structures and properties. Reactivity of a dibismuthane towards elemental sulfur was also investigated, leading to the characterization of dibismuthanyl sulfide compounds formed.