Low-Temperature Isolation of the Bicyclic Phosphinophosphonium Salt [Mes*2P4Cl][GaCl4

Abstract

The reaction of [ClP(μ-PMes*)]2 (1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes*P4(Cl)Mes*][GaCl4] (3[GaCl4]), which incorporates a positively charged phosphonium center within its bicyclic P4 scaffold. The formation of the title compound was studied by means of low-temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods.