2,7-Dimethyl-4,5-bis(trimethylsilyl)octa-2,3,5,6-tetraene

Jones, Peter G.; Bubenitschek, Peter; Hopf, Henning; Stamm, Reiner

doi:10.1107/s1600536802022870

Cited by 4 publications

(3 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The C(9)C(10) bond (1.318(2) Å) is significantly longer than the C(10)C(11) bond (1.306(2) Å); moreover, while the Si(1)−methyl bond lengths are normal (average of the six values is 1.860 Å), the silicon−carbon C(11)−Si(1) distance is slightly longer, 1.9107(13) Å. These values are similar to those previously observed in Me 2 CCC(TMS)−C(TMS)CCMe 2 …”

Section: Resultssupporting

confidence: 85%

“…Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-675654 (13), CCDC-675655 (15), CCDC-688696 (17), CCDC-689382 (20), CCDC-675656 (21), and CCDC-675657 (27). This information is available free of charge from http://www.ccdc.cam.ac.uk.…”

Section: Preparation Of Tetrabenzodihydroquatercyclopentadiene 15mentioning

confidence: 99%

See 1 more Smart Citation

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉

2008

View full text Add to dashboard Cite

The propargylallene 3,3′-biphenylene-1-trimethylsilyl-1-(9-trimethylsilylethynyl)-9H-fluorenylallene, 12, undergoes thermal rearrangement in refluxing THF to the corresponding s-trans-bis(fluorenylidene)bis(trimethylsilyl)diallene, 13. In contrast, when thermolyzed in refluxing toluene, 12 cyclizes to form a cyclopentenylidene carbene that dimerizes to furnish the tetrabenzodihydroquatercyclopentadiene 15. Moreover, treatment of 13 with NaF yields C60H36, 17 (the “parent” analogue of 15), whose C36 backbone can be mapped onto C60 and which represents 60% of the fullerene framework. The ligands 12 and 13 both react with di-iron nonacarbonyl to produce the novel complex 21, in which an (η5-fluorenyl)Fe(CO)2 moiety is linked both directly and via a bridging carbonyl to a cyclopentadiene ring bearing two trimethylsilyl substituents and a spiro-bonded fluorenyl fragment. The proposed mechanism involves rearrangement of a coordinated trimethylsilylalkyne unit into a vinylidene complex prior to formation of the cyclopentadiene ring. However, the complex 21 is relatively unstable and undergoes oxidative decomposition with loss of iron and formation of a bicyclic lactone, 27, possessing two spiro-bonded fluorenyl groups. The X-ray crystal structures of 13, 15, 17, 21, and 27, as well as that of 1,4-bis(fluorenylidene)-2-butyne, 20, are reported.

show abstract

Section: Resultssupporting

confidence: 85%

Section: Preparation Of Tetrabenzodihydroquatercyclopentadiene 15mentioning

confidence: 99%

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉

2008

View full text Add to dashboard Cite

show abstract

“…The highly symmetric derivatives 11 and 12 are again solids, whereas 10 is an oil at room temperature. We have reported on the X-ray analysis of 11 in an earlier study [12]. …”

Section: Resultsmentioning

confidence: 99%

Polar reactions of acyclic conjugated bisallenes

Stamm¹,

Hopf²

2013

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

SummaryThe chemical behaviour of various alkyl-substituted, acyclic conjugated bisallenes in reactions involving polar intermediates and/or transition states has been investigated on a broad scale for the first time. The reactions studied include lithiation, reaction of the thus formed organolithium salts with various electrophiles (among others, allyl bromide, DMF and acetone), oxidation to cyclopentenones and epoxides, hydrohalogenation (HCl, HBr addition), halogenation (Br2 and I2 addition), and [2 + 2] cycloaddition with chlorosulfonyl isocyanate. The resulting adducts were fully characterized by spectroscopic and analytical methods; they constitute interesting substrates for further organic transformations.

show abstract

Organic and Organometallic Derivatives of Propargylallene: Syntheses, Structures, Reactivity and Rearrangements

McGlinchey

Hopf

2013

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

show abstract

2,7-Dimethyl-4,5-bis(trimethylsilyl)octa-2,3,5,6-tetraene

Abstract: Key indicatorsSingle-crystal X-ray study T = 178 K Mean '(C±C) = 0.003 A Ê R factor = 0.042 wR factor = 0.115 Data-to-parameter ratio = 24.9For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 3 publications

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉

Polar reactions of acyclic conjugated bisallenes

Organic and Organometallic Derivatives of Propargylallene: Syntheses, Structures, Reactivity and Rearrangements

Contact Info

Product

Resources

About

2,7-Dimethyl-4,5-bis(trimethylsilyl)octa-2,3,5,6-tetraene

Abstract: Key indicatorsSingle-crystal X-ray study T = 178 K Mean '(C±C) = 0.003 A Ê R factor = 0.042 wR factor = 0.115 Data-to-parameter ratio = 24.9For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 3 publications

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C36 Fragment Corresponding to 60% of C60: Reaction of the Diallene with Fe2(CO)9

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C36 Fragment Corresponding to 60% of C60: Reaction of the Diallene with Fe2(CO)9

Polar reactions of acyclic conjugated bisallenes

Organic and Organometallic Derivatives of Propargylallene: Syntheses, Structures, Reactivity and Rearrangements

Contact Info

Product

Resources

About

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉

Unexpected Dimerization of a Bis(fluorenyl)-bis(trimethylsilyl)-diallene to a Dihydroquatercyclopentadiene, an Octacyclic C₃₆ Fragment Corresponding to 60% of C₆₀: Reaction of the Diallene with Fe₂(CO)₉