The ring-opening polymerization (ROP) of [PCl2N]3 is complicated by the presence of HCl, which is formed via hydrolysis of P-Cl bonds at the high ROP temperatures, or by PCl5, which is a common impurity in [PCl2N]3. We have mapped the potential energy surface of the gas phase reaction of a [PCl2N]3 molecule in the presence of HCl and PCl5 (separately) using DFT calculations at the 6-311G+(d) level of theory and with a B3LYP functional. An associative mechanism that involves a four-center transition state was found for the reaction with PCl5 of [PCl2N]3. With HCl, protonation occurs followed by formation of a reactive NH terminated linear oligomer.

Mechanistic insight into the ring-opening polymerization of [PCl2N]3 in the presence of HCl and PCl5

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