Conformational Control in [22]- and [24]Pentaphyrins(1.1.1.1.1)
by Meso Substituents and their N‑Fusion Reaction
- Publication date
- Publisher
Abstract
<i>meso</i>-Substituted pentaphyrins(1.1.1.1.1) were
unexpectedly isolated as N-fused species under Rothemund-type conditions.
The reaction mechanism is unknown at present, but the first example
of a nonfused [22]pentaphyrin was reported in 2012. Here, the conformational
preferences and N-fusion reaction of [22]- and [24]pentaphyrins have
been investigated using density functional calculations, together
with their aromaticity-molecular topology relationships. Two global
minima are found for the unsubstituted [22]pentaphyrin corresponding
to <i>T0</i> and <i>T0</i><sup>4,D</sup> Hückel
structures. Möbius transition states are located in the interconversion
pathways with activation barriers of 27 kcal mol<sup>–1</sup>. Conversely, [24]pentaphyrin is able to switch between Hückel
and Möbius conformers with very low activation barriers. However,
nonfused [24]pentaphyrins are unstable and spontaneously undergo an
N-fusion reaction driven by the strain release. On the contrary, nonfused
[22]pentaphyrins could be isolated if a <i>T0</i><sup>4,D</sup> conformation is adopted. Importantly, conformational control of
pentaphyrins can be achieved by <i>meso</i>-substituents.
Two stable conformations (<i>T0</i><sup>4,D</sup> and <i>T0</i><sup>A,D</sup>) are found for the nonfused [22]pentaphyrin,
which are delicately balanced by the number of substituents. The <i>T0</i><sup>A,D</sup> conformation is preferred by fully <i>meso</i>-aryl pentaphyrins, which is converted to the N-fused
species. Interestingly, the removal of one aryl group prevents the
N-fusion reaction, providing stable aromatic nonfused [22]pentaphyrins
in excellent agreement with the experimental results