A series of phosphites were prepared bearing various combinations of phenoxy, methoxy, and trifluoroethoxy substituents. (PhO)(3)P, (CF3CH2O)(PhO)(2)P, (CF3CH2O)(2)(PhO)P, and (CH3OCH2CH2O)(PhO)(2)P were polymerized during the course of the Staudinger reaction with azidotrimethylsilane to form low molecular weight polyphosphazenes. Similar reactions with (CH3O)(CF3CH2O)(2)P, (CH3O)(PhO)(2)P, (CH3O)(2)(CF3CH2O)P, (CH3O)(2)(PhO)P, and (CH3O)(3)P produced the desired phosphoranimine as well as the corresponding phosphoramidate isomer. Studies were performed on these systems in order to understand the nature of this isomerization. (CH3O)(PhO)(2)P=N-Si(CH3)(3) and (CH3O)(2)(PhO)P=N-Si(CH3)(3) polymerize at temperatures above 150 degrees C.