Chemistry:Norbornadiene
| |||
| |||
| Names | |||
|---|---|---|---|
| Preferred IUPAC name
Bicyclo[2.2.1]hepta-2,5-diene | |||
| Other names
2,5-Norbornadiene
| |||
| Identifiers | |||
3D model (JSmol)
|
|||
| ChemSpider | |||
| EC Number |
| ||
PubChem CID
|
|||
| UNII | |||
| UN number | 2251 | ||
| |||
| |||
| Properties | |||
| C7H8 | |||
| Molar mass | 92.14 g/mol | ||
| Density | 0.906 g/cm3 | ||
| Melting point | −19 °C (−2 °F; 254 K) | ||
| Boiling point | 89 °C (192 °F; 362 K) | ||
| Insoluble | |||
| Hazards | |||
| GHS pictograms | 
| ||
| GHS Signal word | Danger | ||
| H225 | |||
| P210, P233, P240, P241, P242, P243, P280, P303+361+353, P370+378, P403+235, P501 | |||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |||
 verify (what is   ?)
| |||
| Infobox references | |||
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 [citation needed]
Reactions
Quadricyclane, a valence isomer, can be obtained from norbornadiene by a photochemical reaction when assisted by a sensitizer such as acetophenone:[1]
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.[2]
Norbornadiene is reactive in cycloaddition reactions. Norbornadiene is also the starting material for the synthesis of diamantane[3] 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.[4]
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.[5] 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.[6][7]
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
- ↑ Smith, Claiborune D. (1988). "Quadricyclane". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=cv6p0962.; Collective Volume, 6, pp. 962
- ↑ 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. doi:10.1021/jp972007h. Bibcode: 1997JPCA..101.8834S.
- ↑ Diamantane in Organic Syntheses Coll. Vol. 6, p.378; Vol. 53, p.30 Online Article
- ↑ 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". Molecules 6 (4): 353–369. doi:10.3390/60400353. PMC 6236418. http://www.mdpi.org/molecules/papers/60400353.pdf.
- ↑ 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. http://www.arkat-usa.org/ark/journal/2004/I13_Krohn/1112/KK-1112F.asp.
- ↑ Ryo Shintani, Tamio Hayashi "Chiral Diene Ligands for Asymmetric Catalysis" Aldrich Chimica Acta 2009, vol. 42, number 2, pp. 31-38.
- ↑ 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.
 |  |
