Calicene Explained

Calicene or triapentafulvalene is a hydrocarbon of the fulvalene class with chemical formula C8H6, composed of a cyclopentadiene ring and a cyclopropene ring linked by a double bond. Its name is derived from the Latin calix meaning "goblet", from its shape.

Properties

Very high resonance energy is predicted by the Hückel method,[1] however its resonance energy is not high.The central double bond is polarized with a partial positive charge on the carbon atom of triangular ring and a partial negative charge on the carbon atom of pentagonal ring, in keeping with added Hückel's rule stability of rings containing 2 π electrons and 6 π electrons respectively. Calicene's dipole moment has been computed to be 4.66 D.[2] Several compounds that contains two or more calicene subunits are aromatic, such as trans-bicalicene (ring compound) or poly-2,7-[N]calicenes (chain compound)[3]

Despite several attempts to prepare it, the parent calicene has so far defied attempts at synthesis.[4] However, 1,2,3,4,5,6-hexaphenylcalicene has been prepared and an experimental dipole moment of 6.3 D was measured.[5]

Notes and References

  1. Schaad. L. J. . B. Andes Hess, Jr . Dewar Resonance Energy . Chemical Reviews . 2001 . 101 . 5 . 1465–1476 . 10.1021/cr9903609 . 11710229 .
  2. Oziminski . W. P. . M. Palusia . Capturing the elusive aromaticity of bicalicene . Physical Chemistry Chemical Physics . 2013 . 15 . 9. 3286–3293. 10.1039/C2CP43426A . 23358331 . 2013PCCP...15.3286O.
  3. Ratanadachanakin . Thawalrat . Collier, Willard E. R. . Aromaticity of a series of poly-2,7-[N]calicenes]. Maejo International Journal of Science and Technology . 2015 . 9. 1 . 21–31.
  4. Book: de Meijere, Armin. Houben-Weyl Methods of Organic Chemistry Vol. E 17d, 4th Edition Supplement: Carbocyclic Three-Membered Ring Compounds, Cyclopropenes, Author Index, Compound Index. Georg Thieme Verlag. 2014. 978-3131819741. Stuttgart. 2967.
  5. Agranat. Israel. Bergmann. Ernst D.. 1965-01-01. Hexaphenyltriapentafulvalene. Chemical Communications. en. 21. 512–513. 10.1039/C19650000512. 0009-241X.