Inorganic Chemistry, Vol.45, No.26, 10446-10448, 2006
Phosphazene cations
Cations derived from (NPCl2)(3) hexachloro-cyclo-triphosphazene, the weakly basic precursor of phosphazene polymers, have been prepared using strongly electrophilic reagents based on carborane anions. N-protonated, N-methylated, and N-silylated adducts of (NPCl2)(3) have been isolated and characterized by X-ray crystallographic and spectroscopic methods. The normally potent chloride-abstracting silyl reagents of the type R3Si(carborane) are unable to abstract chloride from (NPCl2)(3), even though the coordinatively unsaturated N2P2Cl5+ cation is widely accepted as a reactive intermediate in the ring-opening polymerization of (NPCl2)(3).