Synthesis and properties of fluoro-derivatives of bis(dichlorophosphinyl)amines

Abstract

Bis(dichlorophosphinyl)amines, [Cl 2P(O)] 2N R, and their fluoro-derivatives, Cl 2P(O)·N R·P(O)ClF, and [F 2P(O)] 2N R ( R = Me, Et, Ph) have been obtained by the condensation of phosphinylamines, X 2P(O)NH R ( X = Cl or F) with phosphoryl halides in the presence of a tertiary amine. A difluoroderivative, [FClP(O)] 2NMe, was obtained as a mixture of diastereoisomers from the reaction of heptamethyldisilazane, (Me 3Si) 2NMe, with FP(O)Cl 2. Attempts to synthesise the P,P-difluoro-derivatives, Cl 2P(O)·N R·P(O)F 2, from difluorophosphinyl amines, F 2P(O)NH R, and phosphoryl chloride or from Cl 2P(O)NH R and F 2P(O)Cl resulted in the formation of impure products and possible reasons for this are discussed. The 1H, 19F and 31P NMR data for these derivatives are given and compared with that for the phosphinylamines, X 2P(O)NH R ( X = F, Cl; R = Me, Et, Ph).