A spirocyclic system comprising both phosphazane and phosphazene rings.

The reaction of hexakis(cyclohexylamino) cyclotriphosphazene [NP(CyNH)(2)](3), 1, with phosphorus trichloride yields [NP(CyN)(2)PCl](3), 2, which contains three four-membered phosphazane rings fused in spirocyclic fashion to a central six-membered phosphazene ring and constitutes the first structurally characterized compound that comprises both phosphazene and phosphazane rings. The peripheral P atoms feature stereoactive lone pairs, and, thus, 2 exists in isomeric C(3h) and C(s) forms. The spirocyclic phosphazene-phosphazane derivative 2 carries three reactive PCl functions in peripheral positions, promising an interesting precursor molecule for the synthesis of extended phosphorus nitrogen structures of high rigidity. Extension of the PN moiety can be achieved by reaction of 2 with a primary amine yielding [NP(CyN)(2)PN(H)(t)Bu](3), 3, which features a central scaffold of 6 phosphorus and 12 nitrogen centers and aggregates via N-H...P hydrogen bonds in the solid state. On the contrary, the reaction of 1 with SbCl(3) undergoes incomplete proton abstraction, resulting in the formation of the tricyclic compound N(3)P(3)(CyNH)(4)(CyNSbCl(2))(2), 4, which contains two four-coordinate Sb centers chelated by N(exo)-N(ring) sites of the phosphazene.