The Effect of Perfluorination on the Aromaticity of Benzene and Heterocyclic Six-Membered Rings

Wu JI, Pühlhofer FG, Schleyer P, Puchta R, Kiran B, Mauksch M, van Eikema Hommes N, Alkorta I, Elguero J (2009)

Publication Status: Published

Publication Type: Journal article

Publication year: 2009

Journal

Publisher: American Chemical Society

Book Volume: 113

Pages Range: 6789-6794

Journal Issue: 24

DOI: 10.1021/jp902983r

Abstract

Despite having six highly electronegative F's, perfluorobenzene C(6)F(6) is as aromatic as benzene. Ab initio block-localized wave function (BLW) computations reveal that both C(6)F(6) and benzene have essentially the same extra cyclic resonance energies (ECREs). Localized molecular orbital (LMO)-nucleus-independent chemical shifts (NICS) grids demonstrates that the F's induce only local paratropic contributions that are not related to aromaticity. Thus, all of the fluorinated benzenes (C(6)F(n)H((6-n)), n = 1-6) have similar ring-LMO-NICS(pi zz) values. However, 1,3-difluorobenzene 2b and 1,3,5-trifluorobenzene 3c are slightly less aromatic than their isomers due to a greater degree of ring charge alternation. Isoelectronic C(5)H(5)Y heterocycles (Y = BH(-), N, NH(+)) are as aromatic as benzene, based on their ring-LMO-NICS(pi zz) and ECRE values, unless extremely electronegative heteroatoms (e.g., Y = O(+)) are involved.

Authors with CRIS profile

Involved external institutions

University of Georgia (UGA) United States (USA) (US) Spanish National Research Council / Consejo Superior de Investigaciones Científicas (CSIC) Spain (ES)

How to cite

APA:

Wu, J.I., Pühlhofer, F.G., Schleyer, P., Puchta, R., Kiran, B., Mauksch, M.,... Elguero, J. (2009). The Effect of Perfluorination on the Aromaticity of Benzene and Heterocyclic Six-Membered Rings. Journal of Physical Chemistry A, 113(24), 6789-6794. https://dx.doi.org/10.1021/jp902983r

MLA:

Wu, Judy I., et al. "The Effect of Perfluorination on the Aromaticity of Benzene and Heterocyclic Six-Membered Rings." Journal of Physical Chemistry A 113.24 (2009): 6789-6794.

BibTeX: Download