The di-tertiary butyl substituted (pseudo-)halogen bismuthanes tBu2BiX (X = Cl, Br, I, CN, N3, SCN) were obtained by different synthetic strategies. They show secondary bonding interactions in the solid state and can be used for the synthesis of ternary group 15 element compounds.

Compounds consisting of [M(1,2-disila-[3n]crown-n)] (M = Mg, Ca, Sr, Ba; n = 5, 6) and [Ba(1,2-disila-benzo[18]crown-6)] cations and different anions were obtained by equimolar reaction of the hybrid disila-crown ethers 1,2-disila[15]crown-5 (1), 1,2-disila[18]crown-6 (2) and 1,2-disila-benzo[18]crown-6 (7) with alkaline earth metal salts. Even with strongly coordinating anions such as Br or I stable complexes could be obtained, showing the good coordination ability of these ligands. The structures of all coordination compounds were determined via single crystal X-ray diffraction (XRD). By means of DFT calculations, the complexation ability of 1,2-disila[15]crown-5 (1) towards magnesium bromide was determined to be considerably higher compared to [15]crown-5. The opposite case was observed in solution as the exchange of calcium cations between [18]crown-6 and 1,2-disila[18]crown-6 (2) was studied via dynamic proton nuclear magnetic resonance (NMR) spectroscopy.

Mismatched complexes of the alkali metals cations Li + and Na + were synthesized from 1,2-disila[18]crown-6 (1 and 2) and of K + from 1,2,4,5-tetrasila[18]crown-6 (4). In these alkali metal complexes, not all crown ether O atoms participate in the coordination, which depicts the coordination ability of the C-, Si/C-, and Si-bonded O atoms. Furthermore, the inverse case-the coordination of the large Ba 2+ ion by the relatively small ligand 1,2-disila[15]crown-5-was investigated, yielding the dinuclear complex 5. This structure represents a first outlook on sandwich complexes based on hybrid crown ethers.

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.

The reaction of partially silicon based crown ethers with BeCl2 yields eight-membered Be–O-heterocycles, which are annulated by two six-membered Be–O-cycles.