The mechanism of the ring-opening polymerization (ROP) of hexachloro triphosphazene ([PCl2N]3) has been studied since the 1960s. We have mapped the potential energy surface of the gas phase reaction of two and three [PCl2N]3 molecules using DFT calculations at the 6-311G+(d) level of theory with a B3LYP functional. Important intermediates were verified at the 6-311G+(2d) level of theory. Unlike the dissociative mechanisms that are usually proposed for the ROP, an associative mechanism that involves a four-center transition state was found. The ring-ring expansion reaction of [PCl2N]3 that gives larger [PCl2N]m ring by-products also appears to be an associative process. If time allows work on the mechanisms of the ROP of [PCl2N]3 in the presence of the additives HCl, PCl5, and MCl3 (M = B, Al, Ga) will be presented.

Mechanistic insight into the ring-opening polymerization of hexachloro triphosphazene

ACS Spring 2022

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