Formation of the spirocyclic, Si-centered cage cations [ClP(NSiMe3)2Si(NSiMe3)2P5](+) and [P5(NSiMe3)2Si(NSiMe3)2P5](2).

On account of our interest in P4 activation by phosphenium ion insertion into P-P bonds we have developed synthetic routes to bicyclic N-P-Si-heterocycle 7 and probed its reactivity towards GaCl3 and P4. A GaCl3-induced rearrangement of 7 leads to the in situ formation of spirocyclic, Si-centered phosphenium ions. Their insertion into P-P bonds of one or two P4 tetrahedra yields polyphosphorus cages [ClP(NSiMe3)2Si(NSiMe3)2P5](+) (19(+)) and [P5(NSiMe3)2Si(NSiMe3)2P5](2+) (13(2+)).