Lewis Acid Assisted Methyl/Chlorine Exchange in Silylated Hydrazinochlorophosphanes

Differently substituted hydrazinophosphanes of the type (Me3Si)2N−N(SiMe3)−PR1R2 (R1 = Cl with R2 = Me, C6F5 and R1 = Me, R2 = C6H5) have been studied in the reaction with Lewis acids such as ECl3 (E = Al, Ga). For (Me3Si)2N−N(SiMe3)−P(Cl)(Me) and (Me3Si)2N−N(SiMe3)−P(Me)(C6H5), only adduct formation was found while a chlorine/methyl exchange reaction was observed for (Me3Si)2N−N(SiMe3)−P(Cl)R (R = C6H5 and C6F5) leading to the formation of (Me2ClSi)(Me3Si)N−N(SiMe3)−P(Me)R, which crystallize as ECl3 adducts. The free hydrazinophosphanes can be obtained by removal of the Lewis acid with the help of a strong base such as 4-(dimethylamino)pyridine (DMAP).