Fulvalene Explained

Fulvalene (bicyclopentadienylidene) is the member of the fulvalene family with the molecular formula C10H8. It is of theoretical interest as one of the simplest non-benzenoid conjugated hydrocarbons. Fulvalene is an unstable isomer of the more common benzenoid aromatic compounds naphthalene and azulene. Fulvalene consists of two 5-membered rings, each with two double bonds, joined by yet a fifth double bond. It has D2h symmetry.

History

An earlier attempt at synthesis of fulvalene in 1951 by Pauson and Kealy resulted in the accidental discovery of ferrocene.[1] Its synthesis was first reported in 1958 by E. A. Matzner, working under William von Eggers Doering.[2] In this method, the cyclopentadienyl anion is coupled with iodine to the dihydrofulvalene. Double deprotonation of the dihydrofulvalene with n-butyllithium gives the dilithio derivative, which is oxidized by oxygen. Fulvalene was spectroscopically observed at 770NaN0 from photolysis of diazocyclopentadiene, which induces dimerization of cyclopentadiene-derived carbenes.[3] The compound was isolated in 1986[4] and was found to be nonaromatic. Above NaNC it dimerizes by a Diels–Alder reaction.

Derivatives

Perchlorofulvalene (C4Cl4C)2 is quite stable in contrast to fulvalene itself.[5]

See also

Notes and References

  1. T. J. Kealy, P. L. Pauson . A New Type of Organo-Iron Compound . Nature . 1951 . 168 . 1039–1040 . 10.1038/1681039b0 . 4285. 1951Natur.168.1039K . 4181383 .
  2. Dissertation Abstracts Int'l 26-06 page 3270 6411876.
  3. 10.1021/ja01531a008. Photochemical Experiments in Rigid Media at Low Temperatures. II. The Reactions of Methylene, Cyclopentadienylene and Diphenylmethylene. 1959. Demore. William B.. Pritchard. H. O.. Davidson. Norman. Journal of the American Chemical Society. 81. 22. 5874–5879.
  4. Synthese von Pentafulvalen durch oxidative Kupplung von Cyclopentadienid mittels Kupfer(II)-chlorid. André. Escher. Werner. Rutsch. Markus. Neuenschwander. Helvetica Chimica Acta. 69. 1644–1654. 1986. 7. 10.1002/hlca.19860690719.
  5. Mark, V. . 10.15227/orgsyn.046.0093. Perchlorofulvalene. Organic Syntheses. 1966. 46. 93.