Chlorophosphazenes have been synthesized since the late 1800s, but there is still speculation and generalization about the various intermediates and products of this synthesis. The mechanisms reported in literature have a similar first step of the synthesis where PCl5 interacts heterogeneously with NH4Cl in solvent and heat to form Cl3P=NH and then the shortest [Cl3P=N-PCl3]+X- cationic linear chlorophosphazene in high yield prior to the second step formation of longer oligomers and cyclic products. Synthetically this is a logical deduction, but historically the Cl3P=NH molecule has never been isolated. There are claims that the Cl3P=NH molecule has been identified analytically from these reactions, and currently literature only cites the synthesis of the [Cl3P=N-PCl3]+X- product in sym-tetrachloroethane (sTCE) or nitrobenzene solvent or through an alternate synthetic route using a Cl3P=NSiMe3 intermediate. Currently we are studying the first step of this mechanism synthetically and by quantum mechanical calculation studies to determine the properties of the Cl3P=NH molecule and various intermediates to better understand of the synthetic chemistry of the chlorophosphazene oligomers.

Chlorophosphazene oligomers; a DFT study of transition states and mechanisms of the initiating step

Macromolecular Chemistry: The Second Century

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