Multiple interpnictogen compounds with covalent single bonds between a diarylbismuth fragment and all lighter pnictogens were obtained from diarylhalido bismuthanes. This includes compounds with a rare Bi–As or Bi–Sb single bond.

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.

Alkali metal dihydrogen-antimonides [M-(L) x SbH 2 ], short: alkali metal antimonides (M = Li, Na, K, Rb, Cs; 1: L = pmdta; 2: L = crown-ether), were prepared from stibine and n-Butyllithium, M(hmds) (hmds = hexamethyldisilazane) or MOtBu, respectively. We developed a generally applicable synthesis route for these compounds and the obtained compounds were examined on their stability depending on the alkali metal and stabilizing additives used, whereby the use of appropriate crown-ethers allowed their isolation and characterization at room temperature. Moreover, the 1,4-dioxane adduct [Na(dioxane) x SbH 2 ] was the appropriate starting compound for the synthesis of the first primary silylstibane (Me 3 Si) 3 SiSbH 2 (3) which was characterized by NMR and IR spectroscopy. Reaction of 3 with (Dipp 2 NacNac)Ga (Dipp 2 NacNac = HC{C-(Me)N(Dipp)} 2 ; Dipp = 2,6-iPr 2 C 6 H 3 ) resulted in the formation of (Dipp 2 NacNac)GaH(SbHSi(SiMe 3 ) 3 ) (4) which was furthermore characterized by single crystal xray diffraction.

The molecular compound [BiDipp2(SbF6)], containing the bulky, donor‐free bismuth cation [BiDipp2]+ has been synthesized and fully characterized (Dipp=2,6‐iPr2‐C6H3). Using its methyl analog [BiMe2(SbF6)] as a second reference point, the impact of steric bulk on bismuth‐based Lewis acidity was investigated in a combined experimental (Gutmann‐Beckett and modified Gutmann‐Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF6]− and neutral Lewis bases such as isocyanides C≡NR’ revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth‐bound isocyanides have been isolated and fully characterized.

Herein, we report about the preparation of several new 2,6diisopropylphenyl (Dipp) substituted (halido-) bismuthanes, namely, Dipp 3 Bi (1) and compounds of the form DippBiX 2 (X=Cl, Br, I; 2-4). The compounds 2-4 show a variety of structural motifs in their solid state structures. Reactivity of 2 towards the nucleophiles LiNMe 2 and MeLi was examined, where mostly scrambling reactions with a preference for two Dipp substituents at bismuth were observed. Therefore, the compounds Dipp 2 BiNMe 2 (5) and Dipp 2 BiMe (6) are the main products of these reactions. Moreover, new interpnictogen compounds with BiÀ N, -P, and -Sb single bonds were prepared. Compound 5 was successfully used as precursor for the preparation of Dipp 2 BiNHtBu (7) and Dipp 2 BiSbMes 2 (8), one of very few isolated compounds with a Bi-Sb single bond. Moreover, bismuthanyl phosphanes bearing functional groups (Dipp 2 BiPtBu(SiMe 3 ) (9), Dipp 2 BiPHtBu (10)) have been prepared. Compound 10 is the first isolated secondary phosphane with a bismuthanyl substituent. All isolated compounds were analyzed via IR and NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X ray diffraction.[a] T.