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Cyclopentadiene

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Title: Cyclopentadiene  
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Cyclopentadiene

Cyclopentadiene
Skeletal formula of cyclopentadiene Spacefill model of cyclopentadiene
Ball and stick model of cyclopentadiene
Identifiers
Abbreviations CPD, HCp
CAS number  YesY
PubChem
ChemSpider  YesY
UNII  YesY
EC number
MeSH
ChEBI  YesY
RTECS number GY1000000
Beilstein Reference 471171
Gmelin Reference 1311
Jmol-3D images Image 1
Properties
Molecular formula C5H6
Molar mass 66.10 g mol−1
Appearance Colourless liquid
Density 0.786 g cm−3
Melting point −90 °C; −130 °F; 183 K
Boiling point 39 to 43 °C; 102 to 109 °F; 312 to 316 K
Acidity (pKa) 16
Basicity (pKb) -2
Structure
Molecular shape Planar[2]
Thermochemistry
Specific
heat capacity
C
115.3 J K−1 mol−1
Std molar
entropy
So298
182.7 J K−1 mol−1
Hazards
Flash point 25 °C (77 °F; 298 K)
Related compounds
Related hydrocarbons Benzene
Cyclobutadiene
Cyclopentene
Related compounds Dicyclopentadiene
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY   YesY/N?)

Cyclopentadiene is an 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

  • International Chemical Safety Card 0857
  • NIOSH Pocket Guide to Chemical Hazards

External links

  1. ^ "1,3-cyclopentadiene - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 16 September 2004. Retrieved 8 October 2011. 
  2. ^ 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.  
  3. ^ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010. ISBN 1-891389-53-X.
  4. ^ a b 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
  5. ^ Robert Bruce Moffett (1962), "Cyclopentadiene and 3-Chlorocyclopentene",  
  6. ^ Streitwieser, A.; Heathcock, C. H.; Kosower, E. M. (1998). Introduction to Organic Chemistry (4th Edn.) Upper Saddle River, NJ: Prentice Hall.
  7. ^ Masaji Oda, Takeshi Kawase, Tomoaki Okada, and Tetsuya Enomoto (1998), "2-Cyclohexene-1,4-dione",  
  8. ^  
  9. ^ Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry. Mill Valley, CA: University Science Books.  
  10. ^ Jolly, W. L. (1970). The Synthesis and Characterization of Inorganic Compounds. Englewood Cliffs, NJ: Prentice-Hall.  
  11. ^ Kolle, U.; Grub, J. (1985). "Permethylmetallocene 5 Reactions of Decamethylruthenium Cations".  
  12. ^ Paquette, L. A.; Wyvratt, M. J. (1974). "Domino Diels–Alder reactions. I. Applications to the rapid construction of polyfused cyclopentanoid systems".  
  13. ^ "Copernicium Video – The Periodic Table of Videos – University of Nottingham". Retrieved 2011-02-22. 

References

See also

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.[13]

Abbreviation

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

Cyclopentadiene is mainly useful as a precursor to Leo Paquette's 1982 dodecahedrane synthesis.[12] The first step involved reductive dimerization of the molecule to give dihydrofulvalene, not simple addition to give dicyclopentadiene.

Uses

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.[11]

NiCl2 + 2 NaC5H5 → Ni(C5H5)2 + 2 NaCl

Metallocenes and related cyclopentadienyl derivatives have been heavily investigated and represent a cornerstone of 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:[9] As typical example, nickelocene forms upon treating nickel(II) chloride with sodium cyclopentadiene in THF.[10]

[(η5-C5H5)Rh(η4-C5H6)], an 18-valence electron mixed-hapticity rhodocene derivative[8] that can form when the rhodocene monomer is protonated.

Metallocene derivatives

The compound is unusually organic synthesis, the preparation of modified cyclopentadienyl ligands, and metallocenes, described in the next section.

Deprotonation

gives the bicyclic peroxide. 2 Cycloaddition of O[7].1,4-benzoquinone such as dienophilesCyclopentadiene readily undergoes other Diels–Alder reactions with
Effect of temperature on rate of dimerization of C5H6
Relative rate Temperature (°C)
0.05 _20
0.5 0
3.5 25
15 40
[4]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.

Diels–Alder reactions

The hydrogen atoms in cyclopentadiene undergo rapid [1,5]-sigmatropic shifts as indicated by 1H NMR spectra recorded at various temperatures.[6] 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.

Sigmatropic rearrangement

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).[4] To obtain cyclopentadiene monomer, commercial dicyclopentadiene is cracked by heating to ~ 180 °C. The monomer is collected by distillation, and used soon thereafter.[5]

Production and reactions

Contents

  • Production and reactions 1
    • Sigmatropic rearrangement 1.1
    • Diels–Alder reactions 1.2
    • Deprotonation 1.3
    • Metallocene derivatives 1.4
  • Uses 2
  • Abbreviation 3
  • See also 4
  • References 5
  • External links 6

[3]

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