Trichlorosilylated tetrelides [(Cl3Si)3E]− have been prepared by adding 1 equiv of a soluble Cl− salt to (Cl3Si)4Si (E=Si) or 4 Si2Cl6/GeCl4 (E=Ge). To assess their donor qualities, the anions [(Cl3Si)3E]− (E=C, Si, Ge) have been treated with BCl3, AlCl3, and GaCl3. Both BCl3 and GaCl3 give 1:1 adducts with the anionic centers. AlCl3 leads to Cl− abstraction from [(Cl3Si)3E]− with formation of (Cl3Si)4E (E=Si or Ge). (Cl3Si)4Ge is cleanly converted to the perhydrogenated (H3Si)4Ge by use of Li[AlH4]. Another case of Cl− abstraction was observed for [(Cl3Si)3Ge⋅GaCl3]−, which reacts with GaCl3 to afford the neutral dimer [(Cl3Si)3Ge−GaCl2]2.

The free cyclohexasilane Si6Cl12 (1) was obtained in 66% yield from the corresponding Cl(-) diadduct [nBu4N]2[1·2Cl] and AlCl3 in C6H6. The substituted cyclohexasilane 1,1-(Cl3Si)2Si6Cl10 (2), however, cannot be liberated from [nBu4N]2[2·2Cl] under comparable reaction conditions. Instead, a mixture of several products was obtained, from which the oligosilane Si19Cl36 (3) crystallized in low yields. X-ray crystallography revealed 3 to consist of two Si5 rings, bridged by one silicon atom. Compound 1 possesses Lewis acidic sites above and below the ring centroid. Competition experiments reveal that their corresponding acid strengths are comparable to that of BCl3. The reaction of 1 with 6 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to a complete breakdown of the cyclic scaffold and furnishes the dichlorosilylene adduct Idipp-SiCl2.

The halosilicates(II) [nBu 4 N] 2 [Si 6 Br 12 ·2Br] and [nBu 4 P] 2 [Si 6 I 12 ·2I] were prepared by mere addition of the appropriate halide salt to the corresponding disilane Si 2 X 6 (X = Br, I). In the first case, the Br 3 Si-substituted derivative [nBu 4 N] 2 [Si 7 Br 14 ·2Br] formed as a second product. We have been able to obtain single crystals of [Ph 4 P] 2 [Si 7 Br 14 ·2Br] by switching the Brsalt from [nBu 4 N]Br to [Ph 4 P]Br. All three compounds, [nBu 4 N] 2 [Si 6 Br 12 ·2Br] (monoclinic, P2 1 /c), [nBu 4 P] 2 [Si 6 I 12 ·2I] (triclinic, P1), and [Ph 4 P] 2 [Si 7 Br 14 ·2Br] (triclinic, P1) were structurally characterized by X-ray crystallography and found to form "inverse sandwich complexes", in which two Xions are located above and below a planarized Si 6 ring. The free periodated cyclohexasilane Si 6 I 12 is accessible from [nBu 4 N] 2 [Si 6 Cl 12 ·2Cl] and BI 3 (1:5 molar ratio; CH 2 Cl 2 ) via a decomplexation/halide-exchange cascade. Si 6 I 12 (monoclinic, C2/c) adopts a

Hexachlorodisilane reacts with diarylmethanones (aryl=C H , 4-MeC H , 4-tBuC H , 4-ClC H , 4-BrC H ) to furnish the corresponding tetraarylethylenes in good yields. The reductive conversion requires temperatures of about 160 °C and reaction times of 60-72 h. In the initial step, the Lewis-basic carbonyl groups likely generate low-valent [SiCl ] as an analogue of [TiCl ] in the classical McMurry reaction. The coupling sequence further proceeds via benzopinacolones, which have been isolated as key intermediates.

Silicone elastomers are usually produced via addition or condensation curing by means of platinum‐ or tin‐based catalysis. The employed catalysts remain in the final rubber and cannot be recovered, thus creating various economic and environmental challenges. Herein, a light‐mediated curing method using multifunctional silacyclopropenes as crosslinker structures was introduced to create an effective alternative to the conventional industrial crosslinking. To evaluate the potential of the photoreaction a model study with small monofunctional silirenes was conducted. These investigations confirmed the required coupling reactivity upon irradiation and revealed an undesired rearrangement formation. Further optimization showed the reaction selectivity to be strongly influenced by the substitution of the three‐membered ring system and the reaction temperature. The synthesis of multifunctional silirenes was described based on the most suitable model compound to create active crosslinker scaffolds for their application in silicone curing. This photo‐controlled process produces catalyst and additive free elastomers from liquid silicones, including hydride‐, hydroxy‐, or vinyl terminated polydimethylsiloxanes.