title: Group 13 Superacid Adducts of [PCl2N]3.
abstract: Irrespective of the order of the addition of reagents, the reactions of [PCl2N]3 with MX3 (MX3 = AlCl3, AlBr3, GaCl3) in the presence of water or gaseous HX give the air- and light-sensitive superacid adducts [PCl2N]3·HMX4. The reactions are quantitative when HX is used. These reactions illustrate a Lewis acid/Brønsted acid dichotomy in which Lewis acid chemistry can become Brønsted acid chemistry in the presence of adventitious water or HX. The crystal structures of all three [PCl2N]3·HMX4 adducts show that protonation weakens the two P-N bonds that flank the protonated nitrogen atom. Variable-temperature NMR studies indicate that exchange in solution occurs in [PCl2N]3·HMX4, even at lower temperatures than those for [PCl2N]3·MX3. The fragility of [PCl2N]3·HMX4 at or near room temperature and in the presence of light suggests that such adducts are not involved directly as intermediates in the high-temperature ring-opening polymerization (ROP) of [PCl2N]3 to give [PCl2N]n. Attempts to catalyze or initiate the ROP of [PCl2N]3 with the addition of [PCl2N]3·HMX4 at room temperature or at 70 °C were not successful.
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Zin-Min
authors.initials: ZM
authors.lastname: Tun
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Amy J
authors.initials: AJ
authors.lastname: Heston
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Panzner
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Scionti
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Doug A
authors.initials: DA
authors.lastname: Medvetz
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Brian D
authors.initials: BD
authors.lastname: Wright
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: Johnson
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Linlin
authors.initials: L
authors.lastname: Li
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Chrys
authors.initials: C
authors.lastname: Wesdemiotis
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Peter L
authors.initials: PL
authors.lastname: Rinaldi
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Wiley J
authors.initials: WJ
authors.lastname: Youngs
authors.affiliation: Department of Chemistry, The University of Akron , Akron, Ohio 44325-3601, United States.
authors.forename: Claire A
authors.initials: CA
authors.lastname: Tessier