The reactivity of silylated amino(dichloro)phosphanes in the presence of silver salts.

New cyclic and acylic phosphorus-nitrogen compounds have been synthesized in reactions of Hyp-N(SiMe3)PCl2 (hypersilyl = Hyp = (Me3Si)3Si) with silver salts of the perfluorinated anions [CF3CO2](-), [CF3SO3](-), and [C6F5](-). Depending on the choice of the silver salt, not only AgCl but also Me3SiCl elimination could be observed, leading to a transient highly reactive 1,3 dipole molecule. This 1,3 dipole molecule was found to be a key species, which can undergo [3 + 2] cyclization, when a dipolarophile such as acetonitrile is present. Also, dimerization or even cyclo-tetramerization are observed. The occurrence of different reaction channels demonstrates that the hypersilyl moiety can act as a highly reactive functional group. All new compounds have been characterized by single-crystal X-ray diffraction studies.