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

Abstract

The 2,6‐diisopropylphenyl (Dipp) substituent is introduced to diaryl bismuth chemistry. Dipp2BiBr (1‐Br) was prepared by a Grignard reaction and subsequently used as precursor for synthesis of the other diaryl halido bismuthanes Dipp2BiX (1‐X, X=F, Cl, I) and the corresponding triflate Dipp2BiOTf (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 tBu2PTMS (TMS=SiMe3) gives access to the interpnictogen compound Dipp2Bi−PtBu2 (4), which shows a rare example of a covalent Bi−P bond.

Trapping reactions with highly unstable hydrides of antimony and bismuth

“…23,31 The Bi-Bi single bond length of 3.002(6) Å is in the same range as is found for (R 2 Bi 2 ) (R = Ph, Mes, Dipp). [32][33][34] As already mentioned, the formation of dibismuthanes, as in compound 2, is frequently observed in reactions of (Dipp 2 NacNac)Ga with different bismuth species. 23,26 Therefore, we have investigated the influence of the steric demand of the substituent R on the products formed in the reactions of (Dipp 2 NacNac)Ga with alkylated and arylated dichlorobismuthanes RBiCl 2 .…”

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

“…In a previous work, we presented the preparation of Dipp 2 BiP t Bu 2 (Dipp = 2,6-di iso propylphenyl-), one of the few examples of compounds with a covalent Bi–P bond. 28 Using a similar approach, I or II react with LiP t Bu 2 in pentane at −50 °C, which gives the desired di- tert -butyl(diarylbismuthanyl)phosphanes 4 and 5 in yields of 70% and 75% (Scheme 3a). Alternatively, 4 and 5 are accessed by a reaction of I or II and P t Bu 2 (SiMe 3 ) in α,α,α-trifluorotoluene (TFT), where a Bi–P bond is formed via the elimination of trimethylsilyl chloride.…”

“…Compounds 4 and 5 show singlets in the 31 P NMR spectra at 75.6 ppm (4) and 61.7 ppm (5), which is in a similar shift range as Dipp 2 BiPtBu 2 (84.3 ppm). 28 Crystals of 4 and 5 suitable for single crystal X-ray diffraction were obtained from a concentrated solution in pentane at −32 °C (4) and in benzene at 5 °C (5), respectively. Compound 4 crystallises in the monoclinic space group P2 1 /n (Fig.…”

“…The bond length of the structurally similar Dipp 2 BiPtBu 2 (269.80 (7) and 270.14(7) pm) is considerably longer than in 4, due to the large Dipp substituents. 28 Compound 5 crystallises with two molecules in the asymmetric unit (Fig. 2b).…”

Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides

“…[33] Other intermolecular short Bi•••Bi contacts in the literature have values of in 3.740(4) Å in (Me 3 Si) 2 BiBi(SiMe 3 ) 2 , 3.834(3)-3.873(3) Å in Bi {Co(CO) 4 } 3 , 3.8988(9) Å in Me 3 Bi or 3.9654(4) Å in Dipp 2 BiI (Dipp = 2,6-di-iso-propyl phenyl) and thus are slightly shorter or as long as the one in 10. [32,[34][35][36] Also similar to 9 is the strain of the As 2 N 2 ring which leads to a fold angle of 143.8(3)°, but in contrast to 9 there is no evidence of different conformations of the molecule in solution, since the signals in the NMR spectra are quite sharp. We assume this difference compared to 9 results from the stronger BiÀ Bi interaction that leads to a stabilising effect of the conformation that is represented in the solid state structure of 10.…”