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]A '''fulvalene''' is a ] obtained by formally ] two ] through a common ] ].<ref>''The Fulvalenes'' Brian Halton Eur. J. Org. Chem. '''2005''', 3391–3414 {{DOI|10.1002/ejoc.200500231}}</ref> The name is derived from the similarly structured ]s which lack one ring. Triapentafulvalene ('''3''') is also known as '''calicene''' as in calix or ] because of its wine-glass appearance. |
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In general, the parent fulvalenes are very unstable and for instance the parent triafulvalene ('''1''') has not even been synthesized. On the other hand stable fulvalenes can be obtained by proper ] or ]. Several members should be stabilized taking into account a dipolar ] with for instance pentaheptafulvalene '''4''', which can be thought of as a ] joined to a ] anion (both stable and ]). In this compound the dipolar structure is calculated to contribute 23% to the total structure. |
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==Pentafulvalene== |
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{{Chembox |
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{{Chembox |
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| verifiedrevid = 443827904 |
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| verifiedrevid = 443829133 |
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| OtherNames = Bicyclopentyliden-2,4,2',4'-tetraene <br /> 1,1'-Bi <br /> Pentafulvalene <br /> Bicyclopentadienylidene <br /> Bicyclopentadienylidene |
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| PIN = -2,2′,4,4′-tetraene |
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| OtherNames = Bicyclopentyliden-2,4,2′,4′-tetraene <br /> 1,1′-Bi <br /> Pentafulvalene <br /> Bicyclopentadienylidene <br /> Bicyclopentadienylidene |
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| ImageFile1 = Fulvalen.png |
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| ImageFile1 = Fulvalen.png |
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| ImageSize1 = 200px |
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| ImageSize1 = 180 |
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| ImageAlt1 = Skeletal formula |
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| ImageFile2 = Pentafulvalene-3D-spacefill.png |
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| ImageSize2 = 180 |
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| ImageAlt2 = Space-filling model |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = XEOSBIMHSUFHQH-UHFFFAOYSA-N |
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| StdInChIKey = XEOSBIMHSUFHQH-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 91-12-3 |
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| CASNo = 91-12-3 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = V2K3QQS6YW |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| C = 10 | H = 8 |
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| C = 10 | H = 8 |
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| Density=1.129 g/ml |
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'''Pentafulvalene''' is the member of the fulvalene family with the ] C<sub>10</sub>H<sub>8</sub>. It is of theoretical interest as one of the simplest ] ] ]s. Fulvalene is an unstable ] of the more common benzenoid aromatic compounds ] and ]. It is also known as '''bicyclopentadienylidene'''. Pentafulvalene consists of two 5-membered rings, each with two ]s, joined by yet a fifth double bond. It has D<sub>2h</sub> ]. |
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'''Fulvalene''' ('''bicyclopentadienylidene''') is the member of the ] with the ] C<sub>10</sub>H<sub>8</sub>. It is of theoretical interest as one of the simplest ] ] ]s. Fulvalene is an unstable ] of the more common benzenoid aromatic compounds ] and ]. Fulvalene consists of two 5-membered rings, each with two ]s, joined by yet a fifth double bond. It has D<sub>2h</sub> ]. |
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== History == |
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An earlier attempt at synthesis of pentafulvalene in 1951 by Pauson and Kealy resulted in the accidental discovery of ].<ref>{{cite journal |
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] and ] (not shown) are complexes of the fulvalene dianion.]] |
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An earlier attempt at synthesis of fulvalene in 1951 by Pauson and Kealy resulted in the accidental discovery of ].<ref>{{cite journal |
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| author = T. J. Kealy, P. L. Pauson |
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| author = T. J. Kealy, P. L. Pauson |
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| title = A New Type of Organo-Iron Compound |
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| title = A New Type of Organo-Iron Compound |
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| year = 1951 |
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| year = 1951 |
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| volume = 168 |
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| volume = 168 |
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| pages = 1039 |
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| pages = 1039–1040 |
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| doi = 10.1038/1681039b0 |
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| doi = 10.1038/1681039b0 |
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| issue=4285| bibcode = 1951Natur.168.1039K |
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| issue=4285}}</ref> Its synthesis was first reported in 1958 by E. A. Matzner at ], working under ].<ref>''Dissertation Abstracts Int'l'' 26-06 page 3270 6411876.</ref> In this method, dissertation only and never published, a ] is coupled with iodine to the dihydrofulvalene which is then doubly ] (]) to the dianion and then oxidized with oxygen. Pentafulvalene was ] observed at 77 ] from ] of ] (] of two cyclopentadiene ]s) <ref>''Photochemical Experiments in Rigid Media at Low Temperatures. II. The Reactions of Methylene, Cyclopentadienylene and Diphenylmethylene'' William B. DeMore, H. O. Pritchard, Norman Davidson ], '''1959''', 81 (22), pp 5874–5879 {{DOI|10.1021/ja01531a008}}</ref> with UV spectra matching those obtained by the Doering group. Final isolation of the compound came in 1984 <ref>''Synthese von Pentafulvalen durch oxidative Kupplung von Cyclopentadienid mittels Kupfer(II)-chlorid'' André Escher, Werner Rutsch, Markus Neuenschwander Helvetica Chimica Acta Volume 69 Issue 7, Pages 1644 - 1654 '''1984''' {{DOI|10.1002/hlca.19860690719}}</ref> via a method similar to that of Doering. The compound was found to be nonaromatic and extremely reactive above −50 °C through ]. |
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| s2cid = 4181383 |
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}}</ref> Its synthesis was first reported in 1958 by E. A. Matzner, working under ].<ref>''Dissertation Abstracts Int'l'' 26-06 page 3270 6411876.</ref> In this method, the ] is coupled with iodine to the dihydrofulvalene. Double ] of the dihydrofulvalene with ] gives the dilithio derivative, which is oxidized by oxygen. Fulvalene was ] observed at {{convert|77|K|C|0|order=flip}} from ] of ], which induces ] of cyclopentadiene-derived ]s.<ref>{{cite journal|doi=10.1021/ja01531a008|title=Photochemical Experiments in Rigid Media at Low Temperatures. II. The Reactions of Methylene, Cyclopentadienylene and Diphenylmethylene|year=1959|last1=Demore|first1=William B.|last2=Pritchard|first2=H. O.|last3=Davidson|first3=Norman|journal=Journal of the American Chemical Society|volume=81|issue=22|pages=5874–5879}}</ref> The compound was isolated in 1986<ref>{{cite journal|title=Synthese von Pentafulvalen durch oxidative Kupplung von Cyclopentadienid mittels Kupfer(II)-chlorid|first1=André|last1=Escher|first2=Werner|last2=Rutsch|first3=Markus|last3=Neuenschwander|journal=Helvetica Chimica Acta|volume=69|page=1644–1654|year=1986|issue=7|doi=10.1002/hlca.19860690719}}</ref> and was found to be nonaromatic. Above {{convert|−50|C|K|0}} it dimerizes by a ]. |
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== Derivatives == |
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Perchlorofulvalene C<sub>10</sub>Cl<sub>8</sub> is quite stable in contrast to the hydrocarbon.<ref>Mark, V. “Perchlorofulvalene” Organic Syntheses, Collected Volume 5, p.901 (1973). http://www.orgsyn.org/orgsyn/pdfs/CV5P0901.pdf</ref> ] is an ]. |
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Perchlorofulvalene (C<sub>4</sub>Cl<sub>4</sub>C)<sub>2</sub> is quite stable in contrast to fulvalene itself.<ref>{{cite journal |author=Mark, V. |doi=10.15227/orgsyn.046.0093|title=Perchlorofulvalene|journal=Organic Syntheses|year=1966|volume=46|page=93}}</ref> |
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==See also== |
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* ]s, (CH=CH)<sub>2</sub>C=CH<sub>2</sub> and substituted derivatives |
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* ], C<sub>2</sub>H<sub>2</sub>S<sub>2</sub>C=CS<sub>2</sub>C<sub>2</sub>H<sub>2</sub> |
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==Fulvalenes as a ligand== |
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:] |
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Fulvalenes forms stable ] complexes that can be formally considered derivatives of the dianion C<sub>10</sub>H<sub>8</sub><sup>2<nowiki>−</nowiki></sup>. In fact as mentioned above, ferrocene was isolated from an attempted synthesis of fulvalene. Many compounds are known, especially for the early transition metals.<ref>Marta González-Maupoey, Vanessa Tabernero and Tomás Cuenca "Early transition metal fulvalene complexes" Coordination Chemistry Reviews 2009, Volume 253, Pages 1854-1881. {{DOI|10.1016/j.ccr.2009.02.013}}</ref> The central C-C bond in some fulvalene complexes break reversibly.<ref>Boese, R. J.; Cammack, K.; Matzger, A. J.; Pflug, K.; Tolman,W. B.; Vollhardt, K. P. C.; Weidman, T. W. "Photochemistry of (Fulvalene)tetracarbonyldiruthenium and Its Derivatives: Efficient Light Energy Storage Devices" Journal of the American Chemistry Society 1997, volume 119, p. 6757-6773. {{DOI|10.1021/ja9707062}}</ref> |
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==References== |
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==References== |
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