1,1,2,2-Tetrakis(2,6-dimethylphenyl)-1,2-disilacyclopropane

Masamune, Satoru; Murakami, S.; Tobita, Hiromi; Williams, David J.

doi:10.1021/ja00364a069

Cited by 72 publications

(16 citation statements)

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“…Nevertheless, they clearly show considerable potential as precursors for more detailed kinetic studies of the chemistry of reactive vinylsiliranes, the key primary intermediates in the reaction of silylenes with conjugated dienes [18,27,28,[42][43][44].…”

Section: Discussionmentioning

confidence: 99%

The photochemistry of a potential diphenylsilylene precursor. Time-resolved spectroscopic studies of the reactivity of a transient vinylsilirane

et al. 2006

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The photochemistry of 3,4-dimethyl-1,1-diphenylsilacyclopent-3-ene (2), a potential precursor to diphenylsilylene (SiPh 2 ), has been studied in hydrocarbon and methanol solution by steady state and laser flash photolysis techniques. The results are consistent with the formation of three major photoproducts: SiPh 2 (ca. 20%), 2,3-dimethyl-1,3-butadiene (DMB; ca. 20%), and 2-methyl-2-(1-methylethenyl)-1,1-diphenylsilirane (9; ca. 75%), the product of formal photochemical (1,3)-sigmatropic rearrangement of 2. Attempts to detect the silylene by laser flash photolysis were unsuccessful, but the vinylsilirane could be easily detected as a long-lived transient exhibiting λ max = 285 nm and lifetime τ = 1.3 s in hexane at 25 • C. The same spectrum is observed in neat methanol solution, where the lifetime of the species is shortened to τ = 36 ms and it is quenched by sodium methoxide and methanesulfonic acid with absolute rate constants of k MeO -= 2.0 × 10 6 M −1 s −1 and k H+ = 2.6 × 10 3 M −1 s −1 , respectively. The photochemistry of 2 is compared to that of the corresponding germanium homologue (1), whose photolysis in solution has been previously shown to afford diphenylgermylene and DMB cleanly and in high yields. The corresponding vinylgermirane (11a), though not detectable as a primary photoproduct from 1 in solution, is the exclusive product of photolysis of 1 in a 3-methylpentane glass at 78 K, where it exhibits an essentially identical UV/vis spectrum to that of 9. The rate constant for its unimolecular thermal isomerization to regenerate 1 is three orders of magnitude larger than that of the corresponding process in the homologous vinylsilirane (9) in hydrocarbon solution at 25 • C.

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Section: Discussionmentioning

confidence: 99%

The photochemistry of a potential diphenylsilylene precursor. Time-resolved spectroscopic studies of the reactivity of a transient vinylsilirane

et al. 2006

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“…1,1,2,2-Tetrakis(2,4,6-trimethylphenyl)-1,2-disilirane was prepared according to the literature method. 18 Mass spectroscopic measurements were carried out on a JEOL JMS SX 102 mass spectrometer and a Bruker MALDI Biflex III. The vis-near-IR absorption spectra were measured on a Shimadzu UV-3150 spectrometer in ODCB.…”

Section: Methodsmentioning

confidence: 99%

Chemical Reactivities of the Cation and Anion of M@C₈₂ (M = Y, La, and Ce)

et al. 2005

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“…While the reaction of diazomethane with the disilene 10 provides the disilirane 68 86 , that between p-tolyldiazomethane and 9 yields the compound 69 87 The reaction of 2,6-dimethylphenyl isocyanide 70 with the disilene 10 gives the disilacyclopropane imine 71 88 , the unusually bright red color of which was the subject of an intensive theoretical investigation (equation 13) 89 .…”

Section: Mes 2 Simentioning

confidence: 99%