1,3,5-Triethylcyclotriphosph(III)azanes and related compounds

Abstract

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.