Cyclopentadiene

Cyclopentadiene
Names
Systematic IUPAC name
Cyclopenta-1,3-diene[1]
Other names
Pentole

Pyropentylene

1,3-Cyclopentadiene[2]
Identifiers
Abbreviations CPD, HCp
471171
542-92-7 Yes
ChEBI CHEBI:30664 Yes
ChemSpider 7330 Yes
EC number 208-835-4
1311
Jmol-3D images Image
MeSH 1,3-cyclopentadiene
PubChem 7612
RTECS number GY1000000
UNII 5DFH9434HF Yes
Properties
Molecular formula
 C5H6
Molar mass 66.10 g·mol−1
Appearance Colourless liquid
Odor irritating, terpene-like[2]
Density 0.786 g cm−3
Melting point −90 °C; −130 °F; 183 K
Boiling point 39 °C; 102 °F; 312 K
insoluble[2]
Vapor pressure 400 mmHg[2]
Acidity (pKa) 16
Basicity (pKb) -2
Structure
Molecular shape Planar[3]
Thermochemistry
Specific
heat capacity (C)
 115.3 J K−1 mol−1
182.7 J K−1 mol−1
Hazards
Flash point 25 °C (77 °F; 298 K)
US health exposure limits (NIOSH):
TWA 75 ppm (200 mg/m3)[2]
TWA 75 ppm (200 mg/m3)[2]
750 ppm[2]
Related compounds
Related hydrocarbons
Benzene
Cyclobutadiene
Cyclopentene
Related compounds
 Dicyclopentadiene
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Cyclopentadiene is an organic compound with the formula C5H6. This colorless liquid has a strong and unpleasant odor. At room temperature, this cyclic diene dimerizes over the course of hours to give dicyclopentadiene via a Diels–Alder reaction. This dimer can be restored by heating to give the monomer.

The compound is mainly used for the production of cyclopentene and its derivatives. It is popularly used as a precursor to the cyclopentadienyl ligand (Cp) in cyclopentadienyl complexes in organometallic chemistry.[4]

Production and reactions

Cyclopentadiene production is usually not distinguished from dicyclopentadiene since they are interconverted. They are obtained from coal tar (about 10 – 20 g/ton) and by steam cracking of Naphtha (about 14 kg/ton).[5] To obtain cyclopentadiene monomer, commercial dicyclopentadiene is cracked by heating to ~ 180 °C. The monomer is collected by distillation, and used soon thereafter.[6]

Sigmatropic rearrangement

The hydrogen atoms in cyclopentadiene undergo rapid [1,5]-sigmatropic shifts as indicated by 1H NMR spectra recorded at various temperatures.[7] Even more fluxional are the derivatives C5H5E(CH3)3 (E = Si, Ge, Sn), wherein the heavier element migrates from carbon to carbon with a low activation barrier.

Diels–Alder reactions

Famously, cyclopentadiene dimerizes via a reversible Diels–Alder reaction. The conversion occurs in hours at room temperature, but the monomer can be stored for days at −20 °C.[5]

Effect of temperature on rate of dimerization of C5H6
Relative rateTemperature (°C)
0.05 _20
0.5 0
3.5 25
15 40

Cyclopentadiene is a highly reactive diene in Diels–Alder reactions because less rotation of the diene double bonds is required to achieve the transition state geometry compared to other dienes.[8] Cycloaddition of O2 gives the bicyclic peroxide.

Deprotonation

The compound is unusually acidic (pKa 16) for a hydrocarbon, a fact explained by the high stability of the aromatic cyclopentadienyl anion, C5H5−. Simple compounds of this anion (such as the commercially available sodium cyclopentadienide) are often depicted as salts, although the free anion is not present in appreciable quantities in solution. Deprotonation can be achieved with a variety of bases, typically sodium hydride or even sodium metal. The anion serves as a nucleophile in organic synthesis, the preparation of modified cyclopentadienyl ligands, and metallocenes, described in the next section.

Metallocene derivatives

Main article: metallocene
[(η5-C5H5)Rh(η4-C5H6)], an 18-valence electron mixed-hapticity rhodocene derivative[9] that can form when the rhodocene monomer is protonated.

Metallocenes and related cyclopentadienyl derivatives have been heavily investigated and represent a cornerstone of organometallic chemistry owing to their high stability. Indeed, the first metallocene characterised, ferrocene, was prepared the way many other metallocenes are prepared: by combining alkali metal derivatives of the form MC5H5 with dihalides of the transition metals:[10] As typical example, nickelocene forms upon treating nickel(II) chloride with sodium cyclopentadiene in THF.[11]

NiCl2 + 2 NaC5H5 → Ni(C5H5)2 + 2 NaCl

Organometallic complexes that include both the cyclopentadienyl anion and cyclopentadiene itself are known, one example of which is the rhodocene derivative produced from the rhodocene monomer in protic solvents.[12]

Uses

Cyclopentadiene is mainly useful as a precursor to cyclopentene and related monomers such as ethylidenenorbornene. Such species are used in the production of specialty polymers. Cyclopentadienyl complexes serve as reagents in organic synthesis. It was also used as the starting material in Leo Paquette's 1982 dodecahedrane synthesis.[13] The first step involved reductive dimerization of the molecule to give dihydrofulvalene, not simple addition to give dicyclopentadiene.

The start of Paquette's 1982 dodecahedrane synthesis. Note the dimerisation of cyclopentadiene in step 1 to dihydrofulvalene.

Abbreviation

The commonly used abbreviation of the cyclopentadienyl anion is Cp. The abbreviation played a part in the naming of copernicium: the original proposal for the element's symbol was also Cp, but because of the abbreviation for this anion and the fact that lutetium was originally named cassiopeium and had Cp for the symbol as well, the symbol for copernicium was changed to Cn.[14]

See also

References

  1. ↑ "1,3-cyclopentadiene - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 16 September 2004. Retrieved 8 October 2011.
  2. ↑ 2.0 2.1 2.2 2.3 2.4 2.5 2.6 "NIOSH Pocket Guide to Chemical Hazards #0170". National Institute for Occupational Safety and Health (NIOSH).
  3. ↑ Valery I. Faustov, Mikhail P. Egorov, Oleg M. Nefedov and Yuri N. Molin (2000). "Ab initio G2 and DFT calculations on electron affinity of cyclopentadiene, silole, germole and their 2,3,4,5-tetraphenyl substituted analogs : structure, stability and EPR parameters of the radical anions". Phys. Chem. Chem. Phys. 2 (19): 4293–4297. doi:10.1039/b005247g.
  4. ↑ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010. ISBN 1-891389-53-X.
  5. ↑ 5.0 5.1 Dieter Hönicke, Ringo Födisch, Peter Claus, Michael Olson "Cyclopentadiene and Cyclopentene" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a08_227
  6. ↑ Robert Bruce Moffett (1962). "Cyclopentadiene and 3-Chlorocyclopentene". Org. Synth.; Coll. Vol. 4, p. 238
  7. ↑ Streitwieser, A.; Heathcock, C. H.; Kosower, E. M. (1998). Introduction to Organic Chemistry (4th Edn.) Upper Saddle River, NJ: Prentice Hall.
  8. ↑ Brian Levandowski and Ken Houk (2015). Theoretical Analysis of Reactivity Patterns in Diels-Alder Reactions of Cyclopentadiene, Cyclohexadiene, and Cycloheptadiene with Symmetrical and Unsymmetrical Dienophiles. doi/abs/10.1021/acs.joc.5b00174
  9. ↑ Fischer, E. O.; Wawersik, H. (1966). "Uber Aromatenkomplexe von Metallen: LXXXVIII. Uber Monomeres und Dimeres Dicyclopentadienylrhodium und Dicyclopentadienyliridium und Uber Ein Neues Verfahren Zur Darstellung Ungeladener Metall-Aromaten-Komplexe". J. Organomet. Chem. (in German) 5 (6): 559–567. doi:10.1016/S0022-328X(00)85160-8.
  10. ↑ Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry. Mill Valley, CA: University Science Books. ISBN 0-935702-48-2.
  11. ↑ Jolly, W. L. (1970). The Synthesis and Characterization of Inorganic Compounds. Englewood Cliffs, NJ: Prentice-Hall. ISBN 0-13-879932-6.
  12. ↑ Kolle, U.; Grub, J. (1985). "Permethylmetallocene 5 Reactions of Decamethylruthenium Cations". J. Organomet. Chem. 289 (1): 133–139. doi:10.1016/0022-328X(85)88034-7.
  13. ↑ Paquette, L. A.; Wyvratt, M. J. (1974). "Domino Diels–Alder reactions. I. Applications to the rapid construction of polyfused cyclopentanoid systems". J. Am. Chem. Soc. 96 (14): 4671–4673. doi:10.1021/ja00821a052.
  14. ↑ "Copernicium Video – The Periodic Table of Videos – University of Nottingham". Retrieved 2011-02-22.

External links