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47159-GB4
The Scope and Chemical Relevance of Anion-Pi Interactions Involving Aromatics: Computational and Solid-State Studies
Michael Adam Lewis, Saint Louis University
Our
proposal outlined three related areas of research on the interaction between
anions and aromatic π-electron
density. We have made significant
progress on all three fronts, as summarized below.
Correlation
Between Anion-Arene Binding Energies and the Polarizability of the Aromatics. We have calculated the anion-arene
binding energies between halo-substituted aromatics and Cl–
and Br– anions and found an excellent correlation with the sum
of the Hammett substituent constants σp
(Σ σp) of the substituted
aromatics. This is an exciting
result, and it coincides with recent studies showing correlation between
Hammett substituent constants and either anion-arene[1]
or arene-arene[2] binding
energies. Given that dispersion
and polarizability are both known to be factors that contribute to the binding
between anions and aromatic π-electron
density, this result suggests that Hammett σp
values describe the polarizability of substituted aromatics. Our ongoing efforts in this area
involve calculating the polarizability values (<α>) of the substituted aromatics, determining how broad the
correlation is between anion-arene binding energies and the Σ σp values of substituted
aromatics, determining if a correlation exists between anion-arene binding
energies and the < α> values of
substituted aromatics, and determining why σp
values seem to be indicative of aromatic polarizability.
Anion
Binding to Transition Metal-Complexed Aromatics. We have calculated the Cl– and Br–
binding of Ar-FeII-Cp complexes (Ar = substituted aromatic; Cp =
cyclopentadienyl anion) where the anion binds to the π-face of the substituted aromatic Ar and compared that to the
anion binding to the FeII center of the complex. We determined the preference for anion-π binding by subtracting the binding energy
when the anion is complexed to the metal from the binding energy when the anion
is complexed to the aromatic π-cloud. This gave the very surprising result
that the preference for anion-π binding
increased with an increase in electron donating groups on the aromatic. A preliminary explanation for this
involves the charge on the FeII center. The greater the electron donating ability of the
substituent, the greater the charge transfer to the FeII, thus
increasing the anion-π binding energy
and decreasing the anion-metal binding.
Our work in this area has also shown a great correlation between the
anion-π binding energy and the Σ σp values of the substituted Ar
group. Ongoing studies in this
area include explaining why electron-donating groups enhance anion-π binding in Ar-FeII-Cp complexes,
expanding the studies to include Ar-RuII-Cp, Ar-FeII(CO)3
and Ar-RuII(CO)3 complexes, and including more
polarizable anions.
Preparation
of Solid-State Host for Anion--π
Binding Studies. The figure
below shows the synthetic approach being employed to prepare a solid-state host
to study anion-π binding. All but two of the steps have been
successfully completed and the products of the completed steps have been
characterized by NMR and mass spectroscopy. We are currently repeating, and improving the yields, of all
reactions leading up to the marcocyclization reaction because this is expected
to be a low-yield reaction. We
expect to have the desired parent product, where the aromatics have all H
atoms, prepared shortly. The
synthetic approach will allow for facile preparation of macrocycles with
differently substituted aromatic appendages via the wide availability of
arene-substituted chloro- and bromo-acetophenones, which are introduced in the
second step. Once we have numerous
substituted analogs prepared we will begin crystallographic studies to
determine what aromatic substitution patterns allow for anion-π binding in the solid-state.
[1] Gil-Ramirez, G.; Escudero-Adan,
E. C.; Benet-Buchholz, J.; Ballester, P.
Angew. Chem. Int. Ed. 2008,
47, 4114-4118.
[2] (a) Wheeler, S. E.; Houk, K.
N. J. Am. Chem. Soc. 2008,
130, 10854-10855. (b) Beg, S.; Waggoner, K.; Ahmad, Y.;
Watt, M.; Lewis, M. Chem. Phys. Lett. 2008, 455,
98-102.