1,3,5-Triethylcyclotriphosph(<small>III</small>)azanes and related compounds

The cyclophosph(III)azanes, (CIPNEt)3, Cl2P4(NEt)5, and the previously reported diphosphinoamine, Cl2P–NEt–PCl2, are formed by suitable variation of the stoicheiometry of a mixture of phosphorus trichloride and ethylamine hydrochloride in refluxing sym-tetrachloroethane solution. Oxo-derivatives of the cyclic products are also formed in low yields, and in the case of (CIPNEt)3, the same oxo-derivatives can be identified as a product of the reaction with oxygen or dimethyl sulphoxide. Both (CIPNEt)3 and bicyclo-Cl2P4(NEt)5 can be converted to the analogous fluorides by reaction with antimony trifluoride. The former also gives (Cl3PNEt)2 on reaction with chlorine. Cyclotriphosph(III)azanes, (CIPNR)3 (R = Me or Et), were obtained in low yield by heating the diphosphinoamines, Cl2P–NR–PCl2. Isomeric forms of the cyclophosph(III)azanes have been distinguished by n.m.r. spectroscopy and their structures are discussed