5 research outputs found
Group 13 Superacid Adducts of [PCl<sub>2</sub>N]<sub>3</sub>
No full textIrrespective
of the order of the addition of reagents, the reactions of [PCl<sub>2</sub>N]<sub>3</sub> with MX<sub>3</sub> (MX<sub>3</sub> = AlCl<sub>3</sub>, AlBr<sub>3</sub>, GaCl<sub>3</sub>) in the presence of water
or gaseous HX give the air- and light-sensitive superacid adducts
[PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub>. The reactions
are quantitative when HX is used. These reactions illustrate a Lewis
acid/Br酶nsted acid dichotomy in which Lewis acid chemistry can
become Br酶nsted acid chemistry in the presence of adventitious
water or HX. The crystal structures of all three [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> adducts show that protonation weakens
the two P鈥揘 bonds that flank the protonated nitrogen atom.
Variable-temperature NMR studies indicate that exchange in solution
occurs in [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub>, even
at lower temperatures than those for [PCl<sub>2</sub>N]<sub>3</sub>路MX<sub>3</sub>. The fragility of [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> 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 [PCl<sub>2</sub>N]<sub>3</sub> to give [PCl<sub>2</sub>N]<sub>n</sub>. Attempts
to catalyze or initiate the ROP of [PCl<sub>2</sub>N]<sub>3</sub> with
the addition of [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> at room temperature or at 70 掳C were not successful
Group 13 Superacid Adducts of [PCl<sub>2</sub>N]<sub>3</sub>
No full textIrrespective
of the order of the addition of reagents, the reactions of [PCl<sub>2</sub>N]<sub>3</sub> with MX<sub>3</sub> (MX<sub>3</sub> = AlCl<sub>3</sub>, AlBr<sub>3</sub>, GaCl<sub>3</sub>) in the presence of water
or gaseous HX give the air- and light-sensitive superacid adducts
[PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub>. The reactions
are quantitative when HX is used. These reactions illustrate a Lewis
acid/Br酶nsted acid dichotomy in which Lewis acid chemistry can
become Br酶nsted acid chemistry in the presence of adventitious
water or HX. The crystal structures of all three [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> adducts show that protonation weakens
the two P鈥揘 bonds that flank the protonated nitrogen atom.
Variable-temperature NMR studies indicate that exchange in solution
occurs in [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub>, even
at lower temperatures than those for [PCl<sub>2</sub>N]<sub>3</sub>路MX<sub>3</sub>. The fragility of [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> 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 [PCl<sub>2</sub>N]<sub>3</sub> to give [PCl<sub>2</sub>N]<sub>n</sub>. Attempts
to catalyze or initiate the ROP of [PCl<sub>2</sub>N]<sub>3</sub> with
the addition of [PCl<sub>2</sub>N]<sub>3</sub>路HMX<sub>4</sub> at room temperature or at 70 掳C were not successful
