|Abstract||The chemistry of polyphosphazenes and their derivatives has gained immense significance in the scientific community. Depending on the substituents, these materials exhibit a wide variety of chemical and physical properties and are potential candidates for many applications. These phosphazenes are often synthesized from organophosphorus compounds that contain silicon-nitrogen functional groups. The wide variety of reactions that can occur at the phosphorous and the facile cleavage of the Si-N bond makes them potential precursors to acyclic, cyclic, and polymeric P-N systems. In this study, we report the synthesis, characterization, and reactivity of some representative examples of three new types of N-SiMe3 functionalized phosphines. The new phosphines were fully characterized by 1H, 13C, and 31P NMR spectroscopy and by elemental analysis. Some oxidation reactions of these phosphines yielded new phosphoranimines which were also fully characterized. These anilinophosphines and their derivatives are being studied as precursors to traditional poly(phosphazenes) and novel poly(phenylenephosphazenes), i.e., new inorganic-organic hybrid polymers in which phosphazene (-R2P=N-) and phenylene (-C6H4-) units alternate along the backbone. Oxidation reactions of some N-silylanilinophosphines and thermal condensation reactions of suitably substituted anilinophosphoranimines appear to form poly(phenylenephosphazenes) that are under further investigation in this laboratory.