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+ (132+).
- This article is part of the themed collection: Phosphorus Chemistry: Discoveries and Advances