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.

中文翻译：

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三苯基膦亚胺取代的硅烷作为“掩蔽”无环亚硅烷基的合成

膦酰亚胺长期以来被认为是过渡金属化学中有用的配体，但在低价硅化学中这些例子相当罕见。因此，在这项工作中，我们报告了三苯基膦亚胺部分作为新型甲硅烷基的配体的实施，该甲硅烷基被捕获为具有环己烯的硅烷。通过与 B( p -Tol ) ₃、HSiEt ₃、N ₂ O 和 NH ₃进行活化反应，我们证明了甲硅烷表现出类似甲硅烷基的行为，使其成为“掩蔽的”甲硅烷基。此外，我们用乙烯、丙烯和反式处理硅烷-丁烯，导致烯烃交换。在乙烯和丙烯的情况下，可以实现将烯烃额外插入到各自硅烷的硅-硅键中。由于反式丁烯的插入是不可行的，我们推测这种反应的范围受到烯烃空间需求的限制。