An Electrophilic Carbene‐Anchored Silylene–Phosphinidene

The cyclic alkyl(amino) carbene‐anchored silylene–phosphinidene was isolated as L−Si−P(:cAAC−Me) (L=benzamidinate) at room temperature, synthesized from the reduction of L−Si(Cl 2 )−P(:cAAC−Me) ( 1 ) using two equivalents of KC 8 . Compound 1 was prepared by the oxidative addition of a chlorophosphinidene to the benzamidinate substituted silylene center. This is the first molecular example of a silylene–phosphinidene characterized by single‐crystal X‐ray structural analysis. Moreover, 1 H, 31 P, and also 29 Si NMR spectroscopic data supported the formulation of the products. The theoretical calculations of compound 2 are in good agreement with the experimental results.