title: The effect of perfluorination on the aromaticity of benzene and heterocyclic six-membered rings.
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.affiliation: Computational Annex, University of Georgia, Athens, Georgia 30602-2525, USA.
authors.forename: Judy I
authors.initials: JI
authors.lastname: Wu
authors.forename: Frank G
authors.initials: FG
authors.lastname: Pühlhofer
authors.forename: Paul von Ragué
authors.initials: Pv
authors.lastname: Schleyer
authors.forename: Ralph
authors.initials: R
authors.lastname: Puchta
authors.forename: Boggavarapu
authors.initials: B
authors.lastname: Kiran
authors.forename: Michael
authors.initials: M
authors.lastname: Mauksch
authors.forename: Nico J R van Eikema
authors.initials: NJ
authors.lastname: Hommes
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.forename: José
authors.initials: J
authors.lastname: Elguero
mesh_terms: D003198:Computer Simulation; D005466:Fluorocarbons / Q000138:chemical synthesis* / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure
chemical_list: D005466:Fluorocarbons; D006571:Heterocyclic Compounds; C003005:hexafluorobenzene