1994
DOI: 10.1002/hc.520050316
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Matrix‐isolation and electronic structure of vinyl‐substituted silylenes and their complexes with bases [1]

Abstract: Vinyl-substituted silylenes, 2,5-bis(methylene)-l -silacyclopentane-l ,l -diyl (1) and 2-methybne-1 -silacyclopentane-1 ,I -diyl (2), generated photochemically from the corresponding trisilanes in 3-methylpentane (3-MP) at 77 K, showed broad bands at 505 INTROD UCTICINGeneration, structure, and reactions of divalent silicon species, silylenes, have been extensively studied as important reactive intermediates both experimentally and theoretically [2]. The electronic structure of silylenes has been discussed m… Show more

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Cited by 14 publications
(5 citation statements)
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“…These observations are consistent with the interpretation that the violet solution contains a silylene(s) absorbing at around 540 nm, which upon addition of THF form(s) a silylene−THF complex. The formation of the complex results in a bathochromic shift of the absorption (unfortunately, we could not identify the exact location of the absorption peak within the broad absorption range of 550−650 nm), as has been previously observed for other silylenes . The identity of the species absorbing at 538 nm (denoted as X) could not be determined but we can exclude several possibilities.…”
Section: Resultsmentioning
confidence: 85%
“…These observations are consistent with the interpretation that the violet solution contains a silylene(s) absorbing at around 540 nm, which upon addition of THF form(s) a silylene−THF complex. The formation of the complex results in a bathochromic shift of the absorption (unfortunately, we could not identify the exact location of the absorption peak within the broad absorption range of 550−650 nm), as has been previously observed for other silylenes . The identity of the species absorbing at 538 nm (denoted as X) could not be determined but we can exclude several possibilities.…”
Section: Resultsmentioning
confidence: 85%
“…Compounds 38 and 39 are interesting because they represent higher analogues of the elusive vinylcarbenes,4951 which are known to rearrange to cyclopropenes. Although vinylsilylenes had been studied before by Barton52,53 and later by Sakurai,54,55 no examples of vinylated germylenes had previously been reported. Removal of PMe 3 both from 38 and from 39 could be achieved either by application of vacuum or by treatment with B(C 6 F 5 ) 3 (Scheme ).…”
Section: Silylated Higher Ylenesmentioning
confidence: 99%
“…Apparently, 2-MeTHF stabilizes silylene 1 more than the dimer. The origin of the solvent effects cannot be attributed, however, to the well-established complexation of silylenes with Lewis bases because the complexation should cause significant blue shift of the n → p transition; in reality, the absorption maximum of 1 and its temperature dependence in both 3-MP/2-MeTHF (95/5) and 2-MeTHF solutions were the same as those in 3-MP. Intermolecular complexation of 1 with 2-MeTHF would be hampered because of the low Lewis acidity of 1 due to the effective intramolecular electron donation by the amino substituents.…”
Section: Referencesmentioning
confidence: 99%