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Norbornadiene

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Norbornadiene
Names
Preferred IUPAC name Bicyclohepta-2,5-diene
Other names 2,5-Norbornadiene
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.004.066 Edit this at Wikidata
EC Number
  • 204-472-0
PubChem CID
UNII
UN number 2251
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C7H8/c1-2-7-4-3-6(1)5-7/h1-4,6-7H,5H2Key: SJYNFBVQFBRSIB-UHFFFAOYSA-N
SMILES
  • C1C2C=CC1C=C2
Properties
Chemical formula C7H8
Molar mass 92.14 g/mol
Density 0.906 g/cm
Melting point −19 °C (−2 °F; 254 K)
Boiling point 89 °C (192 °F; 362 K)
Solubility in water Insoluble
Hazards
GHS labelling:
Pictograms GHS02: Flammable
Signal word Danger
Hazard statements H225
Precautionary statements P210, P233, P240, P241, P242, P243, P280, P303+P361+P353, P370+P378, P403+P235, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distinctive structural property of being a diene that cannot isomerize (isomers would be anti-Bredt alkenes). Norbornadiene is also a useful dienophile in Diels-Alder reactions.

Synthesis

Norbornadiene can be formed by a Diels-Alder reaction between cyclopentadiene and acetylene

Norbornadiene synthesis
Norbornadiene synthesis

Reactions

Quadricyclane, a valence isomer, can be obtained from norbornadiene by a photochemical reaction when assisted by a sensitizer such as acetophenone:

The norbornadiene-quadricyclane couple is of potential interest for solar energy storage when controlled release of the strain energy stored in quadricyclane back to norbornadiene is made possible.

Norbornadiene is reactive in cycloaddition reactions. Norbornadiene is also the starting material for the synthesis of diamantane and sumanene and it is used as an acetylene transfer agent for instance in reaction with 3,6-di-2-pyridyl-1,2,4,5-tetrazine.

As a ligand

Norbornadiene is a versatile ligand in organometallic chemistry, where it serves as a two-electron or four-electron donor. (Norbornadiene)molybdenum tetracarbonyl is used as a source of "Mo(CO)4", exploiting the lability of the diene ligand in this case. which is a useful source of "chromium tetracarbonyl," e.g. in reactions with phosphine ligands.

The norbornadiene analogue of cyclooctadiene rhodium chloride dimer has been used in homogeneous catalysis. Chiral, C2-symmetric dienes derived from norbornadiene have also been described.

See also

  • Norbornane a saturated compound with the same carbon skeleton.
  • Norbornene a compound with the same carbon skeleton, but with one less double bond.

References

  1. Orrego‐Hernández, Jessica; Hölzel, Helen; Quant, Maria; Wang, Zhihang; Moth‐Poulsen, Kasper (2021-10-14). "Scalable Synthesis of Norbornadienes via in situ Cracking of Dicyclopentadiene Using Continuous Flow Chemistry". European Journal of Organic Chemistry. 2021 (38): 5337–5342. doi:10.1002/ejoc.202100795. ISSN 1434-193X.
  2. Smith, Claiborune D. (1988). "Quadricyclane". Organic Syntheses; Collected Volumes, vol. 6, p. 962.
  3. Gregory W. Sluggett; Nicholas J. Turro & Heinz D. Roth (1997). "Rh(III)-Photosensitized Interconversion of Norbornadiene and Quadricyclane". J. Phys. Chem. A. 101 (47): 8834–8838. Bibcode:1997JPCA..101.8834S. CiteSeerX 10.1.1.130.1791. doi:10.1021/jp972007h.
  4. Diamantane in Organic Syntheses Coll. Vol. 6, p.378; Vol. 53, p.30 Online Article Archived 2012-07-28 at the Wayback Machine
  5. Ronald N. Warrener & Peter A. Harrison (2001). "π-Bond Screening in Benzonorbornadienes: The Role of 7-Substituents in Governing the Facial Selectivity for the Diels-Alder Reaction of Benzonorbornadienes with 3,6-Di(2-pyridyl)-s-Tetrazine" (PDF). Molecules. 6 (4): 353–369. doi:10.3390/60400353. PMC 6236418. S2CID 53874105.
  6. Markus Strotmann; Rudolf Wartchow & Holger Butenschön (2004). "High yield synthesis and structures of some achiral and chiral (diphosphine)tetracarbonylchromium(0) chelate complexes with tetracarbonyl(norbornadiene)chromium(0) as complexation reagent". Arkivoc: KK–1112F.
  7. Ryo Shintani, Tamio Hayashi "Chiral Diene Ligands for Asymmetric Catalysis" Aldrich Chimica Acta 2009, vol. 42, number 2, pp. 31-38.
  8. Huang, Yinhua; Hayashi, Tamio (2022). "Chiral Diene Ligands in Asymmetric Catalysis". Chemical Reviews. 122 (18): 14346–14404. doi:10.1021/acs.chemrev.2c00218. PMID 35972018.
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