Synthesis of a Triphenylphosphinimide-Substituted Silirane as a “Masked” Acyclic Silylene

Abstract

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, HSiEt3, N2O, and NH3, 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 trans-butene was not feasible, we surmise that the scope of this reactivity is restricted by the steric demand of the olefin.