Phosphinimides are long known as useful ligands in transition metal chemistry, but examples of these in low-valent silicon chemistry are rather rare. Hence, in this work, we report on the implementation of a triphenylphosphinimide moiety as a ligand of a novel silylene that is trapped as a silirane with cyclohexene. By performing activation reactions with B(p-Tol) 3 , HSiEt 3 , N 2 O, and NH 3 , we demonstrate that the silirane exhibits a silylene-like behavior, making it a "masked" silylene. Furthermore, we treated the silirane with ethylene, propylene, and trans-butene, which led to an olefin exchange. In the case of ethylene and propylene, an additional insertion of the olefin into the silicon−silicon bonds of the respective siliranes could be achieved. As the insertion of transbutene was not feasible, we surmise that the scope of this reactivity is restricted by the steric demand of the olefin.

A method to functionalize Si-H containing substrates with vinyl substituted silacyclopropenes has been developed. This provides an efficient and versatile technique to generate multi-functional silacyclopropene derivatives, ranging from small molecules...

Multifunctional silacyclopropanes act as universal crosslinkers for PDMS-elastomers, which can react via ring-opening or silylene insertion.

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.