Phosphorus–nitrogen compounds. Part XXXVII. The syntheses, properties, and some reactions of (2,2,2-triphenylphosphazen-1-yl)-cyclotriphosphazatrienes and -cyclotetraphosphazatetraenes

Abstract

Hexachlorocyclotriphosphazatriene, N₃P₃Cl₆, some of its dimethylamino-, and phenyl-derivatives, react with triphenylmonophosphazene, HNPPh₃. The first mentioned yields a mono-(N₃P₃Cl₅·NPPh₃), and two non-geminal bis-triphenylphosphazenyl-derivatives, [N₃P₃Cl₄(NPPh₃)₂]. The others give rise to mono-substituted triphenylphosphazenyl-derivatives, the reagent attacking, where possible, at aPCl₂ grouping to give nongeminal products to which structures are assigned. N₃P₃Cl₅·NPPh₃(a) reacts with 2 mol equiv. of dimethylamine to give the geminal isomer, N₃P₃Cl₄(NMe₂)(NPPh₃), containing twoPCl₂ groups, and (b) gives rise to a structurally analogous geminal ethoxy-derivative, N₃P₃Cl₄(OEt)(NPPh₃), when treated with ether in the presence of various Lewis acids. N₄P₄Cl₈ yields with triphenylmonophosphazene, mono-(N₄P₄Cl₇·NPPh₃) and 2,6-di-substituted derivatives, [N₄P₄Cl₆(NPPh₃)₂]. The mechanisms of the above reactions are discussed in the light of the chemical and physical properties of the above and related compounds.