Phosphorus–nitrogen compounds. Part XXXVI. Alkylthio- and arylthio-cyclotetraphosphazatetraenes

Abstract

The reaction of octachlorocyclotetraphosphazatetraene, N₄P₄Cl₈, with sodium thiolates gives the tetrathiocyclo-tetraphosphazatetraenes, N₄P₄Cl₄(SR)₄, and the organic disulphides, R₂S₂. The only exception to the above replacement pattern is the reaction with sodium isobutanethiolate when a trisubstituted derivative, N₄P₄Cl₅(SBuⁱ)₃, is detected. More forcing reaction conditions do not lead to higher thiolated cyclotetraphosphazatetraenes; instead ring scission and formation of trithiophosphites and trithiophosphates is observed. The tetrathio-derivatives, N₄P₄Cl₄(SR)₄, have geminal structures and spectroscopy suggests that the thio-groups have a 2,2,6,6-arrangement.