Reactions of the cyclic diphosphadiazanes (XPNR)(2) (X = Cl, Br; R = 2,6-dimethylphenyl = Dmp, 2,6-diisopropylphenyl = Dipp) with GaX(3) followed by 4-(dimethylamino)pyridine (DMAP) give the corresponding trimers (XPNR)(3). An unusual cyclophosphazanium tetrachlorogallate salt [(DippN)(3)P(3)Cl(2)][GaCl(4)] has been isolated from the reaction of (ClPNDipp)(2) with GaCl(3) and represents an intermediate in the disproportionation process. Dissociation of the gallate ion on reaction of [(DippN)(3)P(3)Cl(2)][GaCl(4)] with DMAP releases a halide ion, which associates with the dicoordinate phosphenium center to give (ClPNDipp)(3). The observations indicate that the presence of medium-sized substituents at nitrogen (R) thermodynamically destabilize the dimer with respect to the trimer, without offering sufficient stabilization of the monomer, as observed for MesNPX (Mes* = 2,4,6-tri-tert-butylphenyl) (Mes* > Dipp > Dmp). Nevertheless, lability of the N-P bond in these derivatives of (XPNR)(2) allows for transformations between dimer and trimer that may include transient existence of the corresponding monomer. Manipulation of substituent steric strain to modify the relative stability of phosphazane oligomers provides a new methodology for diversification of phosphazane chemistry.