Capturing the elusive aromaticity of bicalicene

W. P. Oziminski*, M. Palusiak, J. Dominikowska, T. M. Krygowski, R. W. A. Havenith, C. M. Gibson, P. W. Fowler*

*Bijbehorende auteur voor dit werk

OnderzoeksoutputAcademicpeer review

13 Citaten (Scopus)

Samenvatting

The ring-current aromaticity of the bicalicene molecule arises, in spite of the 16 p carbon perimeter, from strong local diatropic circulations on the two pentagonal rings, as shown by current-density maps computed at the ipsocentric RHF/6-311G** and DFT/6-311G** levels of theory. Conjugated-circuit models cannot capture this pattern of circulation as it arises from 'ionic' contributions in a valence-bond picture. Canonical molecular-orbital analysis reveals a cancellation of paratropic and diatropic frontier-orbital contributions, which explains the difficulties that Huckel-based models have in producing qualitatively correct current-density maps for this molecule. Other measures of aromaticity reflect, to different extents, the dominance of the 'tetraionic' contribution to the aromaticity of this species.

Originele taal-2English
Pagina's (van-tot)3286-3293
Aantal pagina's8
TijdschriftPhysical Chemistry Chemical Physics
Volume15
Nummer van het tijdschrift9
DOI's
StatusPublished - 2013

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