Group 13 Superacid Adducts of [PCl2N]3
详细信息 查看全文
- 作者：Zin-Min Tun ; Amy J. Heston ; Matthew J. Panzner ; Vincenzo Scionti ; Doug A. Medvetz ; Brian D. Wright ; Nicholas A. Johnson ; Linlin Li ; Chrys Wesdemiotis ; Peter L. Rinaldi ; Wiley J. Youngs ; Claire A. Tessier
- 刊名：Inorganic Chemistry
- 出版年：2016
- 出版时间：April 4, 2016
- 年：2016
- 卷：55
- 期：7
- 页码：3283-3293
- 全文大小：463K
- ISSN：1520-510X
文摘
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.