Several Group 13 MX3 Lewis acids have been used as catalysts/initiators in the ring-opening polymerization of [PCl2N]3. Several mechanisms have been proposed to explain the function of the Group 13 Lewis acid. We have mapped the potential energy surface in the gas phase reaction of two [PCl2N]3 molecules in the presence of several MX3 using DFT calculations at the 6-311G+(d) level of theory and with a B3LYP functional. BCl3 and AlCl3 activate the [PCl2N]3 ring in indirect but different ways. In the transition state, BCl3 interacts weakly with a nitrogen atom that is across the ring from the phosphorus atom that undergoes reaction. In contrast, AlCl3 interacts with a chlorine atom that is on a nearby phosphorus atom to that which undergoes reaction. An associative mechanism that involves a four-center transition state was found the reaction of [PCl2N]3 with either BCl3 or AlCl3. GaCl3 was found to be unreactive.

Mechanistic insight into the ring-opening polymerization of [PCl2N]3 in the presence of group 13 Lewis acids

Where thousands of chemistry professionals meet to share ideas and advance scientific and technical knowledge. Spring 2023 abstracts, posters, and presentations will launch at the end of March.

ACS Spring 2023

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.