Fulvenes and substituted fulvenes

Bergmann, Ernst D.

doi:10.1021/cr60251a002

Cited by 218 publications

(106 citation statements)

References 279 publications

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“…Fulvene 16 was also formed when using THF/MeOH as the solvent. However, isolation of compound 16 proved to be difficult due to extensive decomposition, [21] and only a 28 % yield of pure fulvene 16 could be isolated after fast filtration through silica gel. The use of CD 3 OD in the irradiation of complex 11 a resulted in quantitative incorporation of deuterium on the exocyclic double bond, which yielded compound [ 2 H 1 ]-16 as the only reaction product.…”

Section: Resultsmentioning

confidence: 99%

The Electronic Structure and Photochemistry of Group 6 Bimetallic (Fischer) Carbene Complexes: Beyond the Photocarbonylation Reaction

Lage

Fernández

Mancheño

et al. 2010

Chemistry A European J

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The UV spectra of Group 6 metal carbene complexes bearing a CpM(CO)(3) (Cp = cyclopentadienyl) moiety bonded to the carbene carbon atom exhibit a redshift of the absorption maxima at higher wavelengths with respect to the parent monometallic complexes. This redshift is partly due to a higher occupation on the p(z) atomic orbital of the carbene carbon atom. Time-dependent DFT calculations accurately assign this band to a metal-to-ligand charge-transfer transition, thus showing that the presence of a second metal center does not affect the nature of the transition. However, the photochemical reactivity of Group 6 metal carbene complexes bearing a CpM(CO)(3) moiety strongly depends on the nature of this metal fragment. A new photoslippage reaction leading to fulvenes occurs when Mn-derived products 11 a, 11 b, and 12 a are irradiated (both Cr and W derivatives), whereas Re-derived product 11 c behaves like standard Fischer complexes and yields the usual photocarbonylation products. A new photoreduction process occurring in the metallacyclopropanone intermediate is also observed for these complexes. Both computational and deuteration experiments support this unprecedented photoslippage process. The key to this differential photoreactivity seems to be the M-Cp back-donation, which hampers the slippage process for Re derivatives and favors the carbonylation reaction.

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Section: Resultsmentioning

confidence: 99%

The Electronic Structure and Photochemistry of Group 6 Bimetallic (Fischer) Carbene Complexes: Beyond the Photocarbonylation Reaction

Lage

Fernández

Mancheño

et al. 2010

Chemistry A European J

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“…[2,3] Wurden sie ursprünglich als Kuriositäten mit ungewçhnlichen Bindungslängen und -winkeln wahrgenommen, [4] werden Pentafulvalene mittlerweile als Liganden [5] für Übergangs-metalle sowie als Zwei-Elektronen-Akzeptoren unter Entstehung von aromatischen Dianionen verwendet. [6] Während unsubstituiertes Pentafulvalen instabil bei Temperaturen über À78 8C ist, [7] zeigt das perchlorierte Derivat vollständig reversible Redoxeigenschaften.…”

Section: Im Gedenken An Michael Bendikovunclassified

Ein Dominoprozess zu Dibenzopentafulvalenen mittels vierfacher Carbopalladierung

et al. 2013

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“…The field of fulvalene hydrocarbon chemistry has not been the subject of an independent review previously, rather it has be included within reviews [4,5] and book sections [6,7] on the fulvenes. Our own reviews on cycloproparene chemistry have included the (alkylidene)cycloproparenes that also are regarded as benz-annulated fulvalenes.…”

Section: In Late 1968 He Transferred To Victoria University Of Wellinmentioning

confidence: 99%

The Fulvalenes

Halton

2005

Eur J Org Chem

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The fulvalenes are the class of hydrocarbons obtained by formally cross‐conjugating two rings through a common exocyclic double bond. Although the first report of such a compound dates to 1915, study of the series began in earnest only in the 1950s, and even today many of the unsubstituted parent hydrocarbons remain unknown. The following report, the first to specifically address this class of molecules, summarises the information available from research published to the end of 2004 and offers some suggestions for future study. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Fulvenes and substituted fulvenes

Cited by 218 publications

References 279 publications

The Electronic Structure and Photochemistry of Group 6 Bimetallic (Fischer) Carbene Complexes: Beyond the Photocarbonylation Reaction

The Electronic Structure and Photochemistry of Group 6 Bimetallic (Fischer) Carbene Complexes: Beyond the Photocarbonylation Reaction

Ein Dominoprozess zu Dibenzopentafulvalenen mittels vierfacher Carbopalladierung

The Fulvalenes

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