Fulvalene

Summary

Fulvalene
Skeletal formula
Space-filling model
Names
Preferred IUPAC name
[1,1′-Bi(cyclopentylidene)]-2,2′,4,4′-tetraene
Other names
Bicyclopentyliden-2,4,2′,4′-tetraene
1,1′-Bi[cyclopentadienylidene]
Pentafulvalene
Bicyclopentadienylidene
[5,5′]Bicyclopentadienylidene
Identifiers
  • 91-12-3 checkY
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:51994 checkY
ChemSpider
  • 9083553 checkY
  • 10908294
  • DTXSID10447902 Edit this at Wikidata
  • InChI=1S/C10H8/c1-2-6-9(5-1)10-7-3-4-8-10/h1-8H checkY
    Key: XEOSBIMHSUFHQH-UHFFFAOYSA-N checkY
  • InChI=1/C10H8/c1-2-6-9(5-1)10-7-3-4-8-10/h1-8H
    Key: XEOSBIMHSUFHQH-UHFFFAOYAP
  • C=1\C=C/C(/C=1)=C2\C=C/C=C2
Properties
C10H8
Molar mass 128.174 g·mol−1
Density 1.129 g/ml
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

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.

Biferrocene is a complex of the fulvalene dianion.

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, cyclopentadienyl anion is coupled with iodine to the dihydrofulvalene. Double deprotonation of dihydrofulvalene with n-butyllithium gives the dilithio derivative, which oxidizes with oxygen. Fulvalene was spectroscopically observed at −196 °C (77 K) from photolysis of diazocyclopentadiene, which induces dimerization of cyclopentadiene-derived carbenes.[3] The compound was isolated in 1986.[4] It was found to be nonaromatic. Above −50 °C (223 K) it dimerizes by a Diels–Alder reaction.

Derivatives

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

See also

References

  1. ^ T. J. Kealy, P. L. Pauson (1951). "A New Type of Organo-Iron Compound". Nature. 168 (4285): 1039–1040. Bibcode:1951Natur.168.1039K. doi:10.1038/1681039b0. S2CID 4181383.
  2. ^ Dissertation Abstracts Int'l 26-06 page 3270 6411876.
  3. ^ Demore, William B.; Pritchard, H. O.; Davidson, Norman (1959). "Photochemical Experiments in Rigid Media at Low Temperatures. II. The Reactions of Methylene, Cyclopentadienylene and Diphenylmethylene". Journal of the American Chemical Society. 81 (22): 5874–5879. doi:10.1021/ja01531a008.
  4. ^ Escher, André; Rutsch, Werner; Neuenschwander, Markus (1986). "Synthese von Pentafulvalen durch oxidative Kupplung von Cyclopentadienid mittels Kupfer(II)-chlorid". Helvetica Chimica Acta. 69 (7): 1644–1654. doi:10.1002/hlca.19860690719.
  5. ^ Mark, V. (1966). "Perchlorofulvalene". Organic Syntheses. 46: 93. doi:10.15227/orgsyn.046.0093.