Synthesis of the cyclic aluminatophosphazene ring N(PCI2NMe)(2)AlMeCl (5) has been achieved via a skeletal transmetalation reaction between AlMe3 and the boratophosphazene N(PCI2NMe)(2)BCI2 (1). Reaction of 5 with various halogenated Lewis acids such as GaCl3 yielded the fully chlorinated aluminum heterocycle N(PCI2NMe)(2)AlCl2 (8) through a methyl-halogen exchange process. In contrast, treatment of 5 with excess AlMe3 resulted in complete methylation at aluminum to give N(PCI2NMe)(2)AlMe2 (6). Compound 5 was reacted with various Ag+ salts with weakly coordinating anions, including Ag[OSO2CF3), which afforded the triflate-substituted heterocycle N(PCI2NMe)(2)AlMe(OSO2CF3) (9). The reaction of 5 with Ag[BF4] surprisingly produced the previously known fluorinated boratophosphazene N(PCI2NMe)(2)BF2 (10). The transformation of 1 to 5 and then to 10 represents a rare, formally reversible, skeletal transmetalation process involving boron and aluminum. Treatment of 5 with Ag[PF6] led to the insertion of phosphorus in place of aluminum to form the novel zwitterionic fluorinated phosphorus(V) heterocycle N(PCI2NMe)(2)PF4 (11). The ethyl-substituted aluminatophosphazene N(PCI2NMe)(2)AlMeEt (14) reacted cleanly with a 1:1 mixture of [Ph3C][B(C6F5)(4)] and THF to give the novel donor-stabilized alumazine-phosphazene hybrid cation, [7(.)THF](+), as the [B(C6F5)(4)](-) salt [N(PCI2NMe)(2)AlMe-THF][B(C6F5)(4)] (15).