Silylene Reactions with Buta-1,3-diynes: Cycloadditions, Insertions, and Rearrangements

Ostendorf, Detlev; Kirmaier, Lars; Saak, Wolfgang; Marsmann, H.C.; Weidenbruch, Manfred

doi:10.1002/(sici)1099-0682(199912)1999:12<2301::aid-ejic2301>3.0.co;2-e

Cited by 43 publications

(24 citation statements)

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“…Isomers 37 and 46 , where all the hydrogens are replaced by tertiary butyl groups, have been synthesized recently, and a photochemical rearrangement reaction has been observed between these two compounds . In both cases, especially in 46 , the Si−C single bond lengths are slightly shortened compared to the standard bond length.…”

Section: Resultssupporting

confidence: 71%

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Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Saravanan

Sastry

2002

Organometallics

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Computational studies using density functional theory (B3LYP) and coupled cluster (CCSD(T)) method were performed on a large number of isomers of disilabenzene, C4Si2H4. In all, 78 stationary points were identified, wherein 61 of them correspond to the minima on the C4Si2H6 potential energy surface. Although the planar forms correspond to the most stable isomers, several unconventional structures are highly competitive in energy. While the framework is an important factor, the substitution pattern seems to be equally important in deciding the relative stabilities of the isomers of disilabenzenes. The relative energies of valence isomeric forms are compared with those of benzene, silabenzene, and diphosphabenzene isomers. The relative energy orderings of all the isomers are analyzed, and conclusions about the stability are drawn. Several H-bridged isomers were computed to be very stable. Several monocyclic six-membered ring structures, where the 6π-aromaticity is disturbed, also indicated the flatness of the potential energy surface of disilabenzene and their propensity toward high reactivity and facile rearrangements.

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Section: Resultssupporting

confidence: 71%

“…Ando et al have successfully synthesized 40 , which yields 25 and 49 on heating, and proposed the possible common intermediate for both the conversions to be 42 . Even though 37 and 46 are not valence isomers, we have considered them in this study, as their derivatives have been synthesized recently …”

Section: Introductionmentioning

confidence: 99%

Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Saravanan

Sastry

2002

Organometallics

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“…Thus, the 13 C NMR spectrum contained only signals for olefinic skeletal carbon atoms. The 29 Si NMR spectrum is more informative, showing two deshielded signals at 36.70 and 38.99 ppm, in the same range as those for bicyclic systems of the type 5 (Scheme ). , …”

Section: Resultsmentioning

confidence: 92%

“…The analytical and spectral data indicate the formations of the bis(silirene) 7 with an olefinic double-bond linkage. Of high diagnostic value are the 13 C NMR spectrum, showing only signals for olefinic carbon atoms in the low-field part of the spectrum, and the 29 Si NMR spectrum, exhibiting only a high-field signal at −71.88 ppm in the typical range for silirenes with this substitution pattern ,,, (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Silirenes, three-membered-ring compounds containing a silicon atom and a C−C double bond, have been known for more than 25 years. , An Si−Si-linked bis(silirene) as well as the C−C-linked compound 4 were first prepared much later, the latter by double [2 + 1] cycloaddition of the silylene 2 , generated photolytically from the cyclotrisilane 1 , to the triple bonds of the 1,3-diyne. Compound 4 is thermally stable but undergoes rearrangement to afford the bicyclic system 5 upon renewed photolysis (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Silylenes with Acetylenes and 1,3-Diacetylenes Linked by C−C Multiple-Bond Units¹^,²

et al. 2002

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The reaction of di-tert-butylsilylene (2), generated photochemically from hexa-tertbutylcyclotrisilane (1), with a (Z)-3-hexene-1,5-diyne furnishes a product built up of two silirene rings linked by an olefinic double bond. A similar reaction of 2 with (Z)-6-dodecene-2,4,8,10-tetrayne yields two rearranged 2,5-disilabicyclo[2.2.0]hexane-1(6),3-diene units linked by a C-C double bond. The oligoene frameworks of both compounds adopt the alltrans configuration. Treatment of 1,3,5-tris((trimethylsilyl)ethynyl)benzene and 1,2-diethynylbenzene with 1 affords a 1,3,5-tris(silacyclopropenyl)benzene and a 1H-indeno[2,1-b]silete derivative with an exocyclic tBu 2 SiH group at position 7 of the tricyclic system.

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trans-1,1-Di-tert-butyl-2,3-dimethylsilirane

Parquette

2004

Encyclopedia of Reagents for Organic Synthesis

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Silylene Reactions with Buta-1,3-diynes: Cycloadditions, Insertions, and Rearrangements

Cited by 43 publications

References 26 publications

Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Reactions of Silylenes with Acetylenes and 1,3-Diacetylenes Linked by C−C Multiple-Bond Units¹^,²

trans-1,1-Di-tert-butyl-2,3-dimethylsilirane

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Silylene Reactions with Buta-1,3-diynes: Cycloadditions, Insertions, and Rearrangements

Cited by 43 publications

References 26 publications

Isomers of Disilabenzene (C4Si2H6): A Computational Study

Isomers of Disilabenzene (C4Si2H6): A Computational Study

Reactions of Silylenes with Acetylenes and 1,3-Diacetylenes Linked by C−C Multiple-Bond Units1,2

trans-1,1-Di-tert-butyl-2,3-dimethylsilirane

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Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Isomers of Disilabenzene (C₄Si₂H₆): A Computational Study

Reactions of Silylenes with Acetylenes and 1,3-Diacetylenes Linked by C−C Multiple-Bond Units¹^,²