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.