Difference between revisions of "Cycloocta-1,5-diene"

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Cycloocta-1,5-diene can be prepared by dimerization of [[butadiene]] in the presence of a nickel catalyst, a coproduct being vinylcyclohexene.  Approximately 10,000 tons were produced in 2005.<ref>{{citation | first1 = Thomas | last1 = Schiffer | first2 = Georg | last2 = Oenbrink | contribution = Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene | title = Ullmann’s Encyclopedia of Industrial Chemistry | year = 2005 | publisher = Wiley-VCH | location = Weinheim}}.</ref>
 
Cycloocta-1,5-diene can be prepared by dimerization of [[butadiene]] in the presence of a nickel catalyst, a coproduct being vinylcyclohexene.  Approximately 10,000 tons were produced in 2005.<ref>{{citation | first1 = Thomas | last1 = Schiffer | first2 = Georg | last2 = Oenbrink | contribution = Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene | title = Ullmann’s Encyclopedia of Industrial Chemistry | year = 2005 | publisher = Wiley-VCH | location = Weinheim}}.</ref>
  
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==Reactions and applications==
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==Organic reactions==
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===Organic reactions===
 
 
COD reacts with borane to give [[9-Borabicyclononane|9-borabicyclo[3.3.1]nonane]], commonly known as 9-BBN, a [[reagent]] in organic chemistry used in [[hydroboration]]s.  COD adds SCl<sub>2</sub> (or similar reagents) to give 2,6-dichloro-9-thiabicyclo[3.3.1]nonane:<ref>{{OrgSynth | first = Roger | last = Bishop | title = 9-Thiabicyclo&#91;3.3.1&#93;nonane-2,6-dione | prep = CV9P0692 | volume = 70 | pages = 120 | year = 1992 | collvol = 9 | collvolpages = 692}}. {{citation | first1 = David D. | last1 = Díaz | first2 = Antonella | last2 = Converso | first3 = K. B. | last3 = Sharpless | first4 = M. G. | last4 = Finn | title = 2,6-Dichloro-9-thiabicyclo&#91;3.3.1&#93;nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold | journal = Molecules | year = 2006 | volume = 11 | pages = 212–18| doi = 10.3390/11040212}}.</ref>
 
COD reacts with borane to give [[9-Borabicyclononane|9-borabicyclo[3.3.1]nonane]], commonly known as 9-BBN, a [[reagent]] in organic chemistry used in [[hydroboration]]s.  COD adds SCl<sub>2</sub> (or similar reagents) to give 2,6-dichloro-9-thiabicyclo[3.3.1]nonane:<ref>{{OrgSynth | first = Roger | last = Bishop | title = 9-Thiabicyclo&#91;3.3.1&#93;nonane-2,6-dione | prep = CV9P0692 | volume = 70 | pages = 120 | year = 1992 | collvol = 9 | collvolpages = 692}}. {{citation | first1 = David D. | last1 = Díaz | first2 = Antonella | last2 = Converso | first3 = K. B. | last3 = Sharpless | first4 = M. G. | last4 = Finn | title = 2,6-Dichloro-9-thiabicyclo&#91;3.3.1&#93;nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold | journal = Molecules | year = 2006 | volume = 11 | pages = 212–18| doi = 10.3390/11040212}}.</ref>
 
[[Image:CODSCl2.png|center|400px|2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, synthesis and reactions]]
 
[[Image:CODSCl2.png|center|400px|2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, synthesis and reactions]]
 
The resulting dichloride can be further modified as the di-[[azide]] or di-[[cyano]] derivative in a [[nucleophilic substitution]] aided by [[anchimeric assistance]].
 
The resulting dichloride can be further modified as the di-[[azide]] or di-[[cyano]] derivative in a [[nucleophilic substitution]] aided by [[anchimeric assistance]].
  
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===Metal complexes===
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==Metal complexes==
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1,5-COD typically binds to low-valence metals via both alkene groups. The complex [[Nickel bis(cyclooctadiene)|Ni(cod)<sub>2</sub>]] is a precursor to several nickel(0) and Ni(II) complexes. Metal-COD complexes are attractive because they are sufficiently stable to be isolated, often being more robust than related ethylene complexes.  The stability of COD complexes is attributable to the [[chelate effect]].  The COD ligands are easily displaced by other ligands, such as phosphines.
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[[Image:M(cod)2.png|thumb|150px|right|Structure of M(cod)<sub>2</sub> for M = Ni, Pd, Pt.]]
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:[[Image:M(cod)2.png|thumb|150px|right|Structure of M(cod)<sub>2</sub> for M = Ni, Pd, Pt.]]
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Extensive work has been reported on complexes of COD, much of which can has been described in volumes&nbsp;25, 26, and 28 of ''[[Inorganic Syntheses]]''. COD typically binds to low-valence metals via both alkene groups. Metal-COD complexes are attractive because they are sufficiently stable to be isolated, often being more robust than related ethylene complexes.  The stability of COD complexes is attributable to the [[chelate effect]], but the COD ligands are easily displaced by other ligands, such as phosphines. In chemical formulae, when cyclooctadiene is acting as a [[ligand]], it is conventional to write the abbreviation in lowercase, eg [Ni(cod)<sub>2</sub>].<ref>{{RedBook2005 | rule = IR-4.4.4 and Table&nbsp;VII | pages = 63, 261–68}}.</ref>
  
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Ni(cod)<sub>2</sub> is prepared by reduction of [[anhydrous]] nickel [[acetylacetonate]] in the presence of the ligand, using [[triethylaluminium]].<ref>{{citation | first1 = R. A. | last1 = Schunn | first2 = S. D. | last2 = Ittel | first3 = M. A. | last3 = Cushing | first4 = R. | last4 = Baker | first5 = R. J. | last5 = Gilbert | first6 = D. P. | last6 = Madden | title = Bis(1,5-Cyclooctadiene)Nickel(0) | journal = Inorg. Synth. | volume = 28 | year = 1990 | pages = 94 | doi = 10.1002/9780470132593.ch25}}.</ref>
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The complex [[Nickel bis(cyclooctadiene)|Ni(cod)<sub>2</sub>]] is a precursor to several nickel(0) and Ni(II) complexes. Ni(cod)<sub>2</sub> is prepared by reduction of [[anhydrous]] nickel [[acetylacetonate]] in the presence of the ligand, using [[triethylaluminium]].<ref>{{citation | first1 = R. A. | last1 = Schunn | first2 = S. D. | last2 = Ittel | first3 = M. A. | last3 = Cushing | first4 = R. | last4 = Baker | first5 = R. J. | last5 = Gilbert | first6 = D. P. | last6 = Madden | title = Bis(1,5-Cyclooctadiene)Nickel(0) | journal = Inorg. Synth. | volume = 28 | year = 1990 | pages = 94 | doi = 10.1002/9780470132593.ch25}}.</ref>
 
:1/3[Ni(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>2</sub>]<sub>3</sub>  +  2COD  +  2Al(C<sub>2</sub>H<sub>5</sub>)<sub>3</sub>  →  Ni(cod)<sub>2</sub>  +  2Al(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)  +  C<sub>2</sub>H<sub>4</sub>  +  C<sub>2</sub>H<sub>6</sub>
 
:1/3[Ni(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>2</sub>]<sub>3</sub>  +  2COD  +  2Al(C<sub>2</sub>H<sub>5</sub>)<sub>3</sub>  →  Ni(cod)<sub>2</sub>  +  2Al(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)  +  C<sub>2</sub>H<sub>4</sub>  +  C<sub>2</sub>H<sub>6</sub>
  
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:Li<sub>2</sub>C<sub>8</sub>H<sub>8</sub>  +  PtCl<sub>2</sub>(cod)  +  3C<sub>7</sub>H<sub>10</sub> → [Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub>] +  2LiCl  +  C<sub>8</sub>H<sub>8</sub>  +  C<sub>8</sub>H<sub>12</sub>
 
:Li<sub>2</sub>C<sub>8</sub>H<sub>8</sub>  +  PtCl<sub>2</sub>(cod)  +  3C<sub>7</sub>H<sub>10</sub> → [Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub>] +  2LiCl  +  C<sub>8</sub>H<sub>8</sub>  +  C<sub>8</sub>H<sub>12</sub>
 
:Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub> + 2COD  →  Pt(cod)<sub>2</sub>  +  3C<sub>7</sub>H<sub>10</sub>
 
:Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub> + 2COD  →  Pt(cod)<sub>2</sub>  +  3C<sub>7</sub>H<sub>10</sub>
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The platinum complex has been used in many syntheses:
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Extensive work has been reported on complexes of COD, much of which can has been described in volumes&nbsp;25, 26, and 28 of ''[[Inorganic Syntheses]]''. The platinum complex has been used in many syntheses:
 
 
:Pt(cod)<sub>2</sub>  +  3 C<sub>2</sub>H<sub>4</sub>  →  Pt(C<sub>2</sub>H<sub>4</sub>)<sub>3</sub>  +  2COD
 
:Pt(cod)<sub>2</sub>  +  3 C<sub>2</sub>H<sub>4</sub>  →  Pt(C<sub>2</sub>H<sub>4</sub>)<sub>3</sub>  +  2COD
  

Revision as of 08:43, 24 August 2009

1,5-Cyclooctadiene
Skeletal formula of 1,5-cyclooctadiene
Ball-and-stick model of 1,5-cyclooctadiene
Identifiers
InChI InChI=1/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7-
InChIKey VYXHVRARDIDEHS-QGTKBVGQBM
Standard InChI InChI=1S/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7-
Standard InChIKey VYXHVRARDIDEHS-QGTKBVGQSA-N
CAS number [111-78-4]
EC number 203-907-1
ChemSpider 74815
Properties[1][2][3]
Chemical formula C8H12
Molar mass 108.18 g/mol
Appearance colorless liquid
Density 0.8818 g/ml, liquid (25 ºC)
Melting point

-69.35 ºC[note 1]

Boiling point

151 °C

Solubility in water 0.00641 g/100 ml (25 ºC, est.)
Solubility soluble in benzene
log P 3.16
Vapor pressure 650 Pa (25 ºC)
Refractive index (nD) 1.4905
Hazards[2][4]
EU index number not listed
GHS pictograms Flam. Liq. 3Skin Irrit. 2, Eye Irrit. 2, Skin Sens. 1Aq. Tox. (acute) 1
GHS signal word WARNING
GHS hazard statements H226, H315, H319, H317, H400
GHS precautionary statements P210, P233, P240, P241, P242, P243, P261, P264, P272, P273, P280, P302+352, P303+361+353, P305+351+338
Flash point 35 ºC (95 ºF)
Autoignition temp. 207 ºC (431 ºF)
Explosive limits 1.0–8.6% (est.)
Related compounds
Other compounds Cyclooctene
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)

Cycloocta-1,5-diene is the organic compound with the chemical formula C8H12. Generally abbreviated COD, this diene is a useful precursor to other organic compounds and serves as a ligand in organometallic chemistry.[5][6]

Synthesis

Cycloocta-1,5-diene can be prepared by dimerization of butadiene in the presence of a nickel catalyst, a coproduct being vinylcyclohexene. Approximately 10,000 tons were produced in 2005.[7]

Organic reactions

COD reacts with borane to give 9-borabicyclo[3.3.1]nonane, commonly known as 9-BBN, a reagent in organic chemistry used in hydroborations. COD adds SCl2 (or similar reagents) to give 2,6-dichloro-9-thiabicyclo[3.3.1]nonane:[8]

2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, synthesis and reactions

The resulting dichloride can be further modified as the di-azide or di-cyano derivative in a nucleophilic substitution aided by anchimeric assistance.

Metal complexes

Structure of M(cod)2 for M = Ni, Pd, Pt.

Extensive work has been reported on complexes of COD, much of which can has been described in volumes 25, 26, and 28 of Inorganic Syntheses. COD typically binds to low-valence metals via both alkene groups. Metal-COD complexes are attractive because they are sufficiently stable to be isolated, often being more robust than related ethylene complexes. The stability of COD complexes is attributable to the chelate effect, but the COD ligands are easily displaced by other ligands, such as phosphines. In chemical formulae, when cyclooctadiene is acting as a ligand, it is conventional to write the abbreviation in lowercase, eg [Ni(cod)2].[9]

The complex Ni(cod)2 is a precursor to several nickel(0) and Ni(II) complexes. Ni(cod)2 is prepared by reduction of anhydrous nickel acetylacetonate in the presence of the ligand, using triethylaluminium.[10]

1/3[Ni(C5H7O2)2]3 + 2COD + 2Al(C2H5)3 → Ni(cod)2 + 2Al(C2H5)2(C5H7O2) + C2H4 + C2H6

The related Pt(cod)2 is prepared by a more circuitous route involving the dilithium cyclooctatetraene:[11]

Li2C8H8 + PtCl2(cod) + 3C7H10 → [Pt(C7H10)3] + 2LiCl + C8H8 + C8H12
Pt(C7H10)3 + 2COD → Pt(cod)2 + 3C7H10

The platinum complex has been used in many syntheses:

Pt(cod)2 + 3 C2H4 → Pt(C2H4)3 + 2COD

COD complexes are useful as starting materials, one noteworthy example is the reaction:

Ni(cod)2 + 4CO ⇌ Ni(CO)4 + 2COD

The product Ni(CO)4 is highly toxic, thus it is advantageous to generate it in the reaction vessel as opposed to being dispensed directly. Other low-valent metal complexes of COD include Mo(cod)(CO)4, [RuCl2(cod)]n, and Fe(cod)(CO)3. COD is an especially important in the coordination chemistry of rhodium(I) and iridium(I), examples being Crabtree's catalyst and cyclooctadiene rhodium chloride dimer. The square planar complexes [M(cod)2]+ are known (M = Rh, Ir).

Footnotes

  1. ↑ There is disagreement between sources as to the melting point of cycloocta-1,5-diene: Weast (1981) gives -70 ºC, while CHRIP (quoting a later edition of the CRC Handbook) gives -56.4 ºC. This value is from Ott et al. (1974), with an measurement uncertainty (estimated by the Thermodynamics Research Center, NIST Boulder Laboratories) of 0.06 K.

References

  1. ↑ CRC Handbook of Chemistry and Physics, 62nd ed.; Weast, Robert C., Ed.; CRC Press: Boca Raton, FL, 1981; p C-255. ISBN 0-8493-0462-8.
  2. ↑ 2.0 2.1 Chemical Risk Information Platform (CHRIP), <http://www.safe.nite.go.jp/english/db.html> (accessed 24 August 2009), National Institute of Technology and Evaluation (Japan).
  3. ↑ Ott, J. Bevan; Goates, J. Rex; Reeder, Joan Solid + liquid phase equilibria and solid-compound formation in hexafluorobenzene + cyclic hydrocarbons containing one or two pi-bonds. J. Chem. Thermodyn. 1974, 6 (3), 281–85. DOI: 10.1016/0021-9614(74)90181-5.
  4. ↑ HSNO Chemical Classification Information Database, <http://www.ermanz.govt.nz/Chemicals/ChemicalDisplay.aspx?SubstanceID=1536> (accessed 24 August 2009), New Zealand Environmental Risk Management Authority.
  5. ↑ Buehler, C.; Pearson, D. Survey of Organic Syntheses; Wiley-Interscience: New York, 1970.
  6. ↑ Shriver, Deward F.; Atkins, Peter W. Inorganic Chemistry; W. H. Freeman: New York, 1999.
  7. ↑ Schiffer, Thomas; Oenbrink, Georg Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH: Weinheim, 2005.
  8. ↑ Bishop, Roger 9-Thiabicyclo[3.3.1]nonane-2,6-dione. Org. Synth. 1992, 70, 120, <http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV9P0692>; Coll. Vol., 9, 692. Díaz, David D.; Converso, Antonella; Sharpless, K. B.; Finn, M. G. 2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold. Molecules 2006, 11, 212–18. DOI: 10.3390/11040212.
  9. ↑ Rule IR-4.4.4 and Table VII. In Nomenclature of Inorganic Chemistry; IUPAC Recommendations 2005; Royal Society of Chemistry: Cambridge, 2005; pp 63, 261–68. ISBN 0-85404-438-8, <http://www.iupac.org/publications/books/rbook/Red_Book_2005.pdf>.
  10. ↑ Schunn, R. A.; Ittel, S. D.; Cushing, M. A.; Baker, R.; Gilbert, R. J.; Madden, D. P. Bis(1,5-Cyclooctadiene)Nickel(0). Inorg. Synth. 1990, 28, 94. DOI: 10.1002/9780470132593.ch25.
  11. ↑ Crascall, Louise E.; Spencer, John L.; Doyle, Ruth Ann; Angelici, Robert J. Olefin Complexes of Platinum. Inorg. Synth. 1990, 28, 126. DOI: 10.1002/9780470132593.ch34.

External links

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