Reactions of an equimolar amount of 4-(dimethylamino)pyridine (dmap) with several Al−E heterocycles [R 2 AlE(SiMe 3 ) 2 ] x (E = P, As; R = Me, x = 3; R = Et, x = 2) and Ga−Sb heterocycles [R 2 GaSb(SiMe 3 ) 2 ] x (R = Me, x = 3; R = Et, x = 2) in hexane offers a general pathway for the formation of mono-