The first spectroscopic detection of silaylides in the reaction of dimesitylsilylene with phosphorus, sulfur, and nitrogen-containing substrates. The stability of silaylides

Andō, Wataru; Sekiguchi, Akira; Hagiwara, Kazuyoshi; Sakakibara, Akihito; Yoshida, H.

doi:10.1021/om00092a052

Cited by 59 publications

(23 citation statements)

References 4 publications

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“…Results were also found that were consistent with silanone-to-silylene 194 and silylene-tosilanone-to-silylene 143 …”

Section: Mementioning

confidence: 55%

“…Trapping of the silylenes by the ether was shown to compete with silylene dimerization, and the silylene ether complexes displayed a different reactivity from the free silylenes. Spectra of silylene complexes with N, O, P and S n-donor bases pyrrolidine, Nmethylpyrrolidine, piperidine, tetrahydrofuran, tetrahydrothiophene, and Bu 3 P have also been reported (see Section V.A.2) 113,143 .…”

Section: Recently Discovered Addition Reactionsmentioning

confidence: 99%

“…Later experiments were undertaken in mixed matrices containing 95% 3-MP and 5% Lewis base 113,143 . Irradiation of the trisilane precursors at 77 K gave initially the silylenes,…”

Section: Silylene Lewis Acid Complexesmentioning

confidence: 99%

“…Representative data for absorption maxima of three silylenes with several bases are given in Table 4. The frequency shift upon complexation depends on the nature of both the base and the silylene and should be a measure of the strength of the interaction 113,143 . For the comparison of bases, the data for Me 2 Si are most appropriate, since the silylene is unhindered.…”

Section: Silylene Lewis Acid Complexesmentioning

confidence: 99%

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Silylenes

Gaspar¹,

West²

2009

Patai's Chemistry of Functional Groups

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Introduction Generation of Silylenes Reactions of Silylenes Theoretical Calculations Spectroscopic Characterization of Silylenes Kinetics of Silylene Reactions Silylene–Transition Metal Complexes Special Topics Speculations on the Future of Silylene Chemistry

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“…Results were also found that were consistent with silanone-to-silylene 194 and silylene-tosilanone-to-silylene 143 …”

Section: Mementioning

confidence: 55%

Section: Recently Discovered Addition Reactionsmentioning

confidence: 99%

“…Later experiments were undertaken in mixed matrices containing 95% 3-MP and 5% Lewis base 113,143 . Irradiation of the trisilane precursors at 77 K gave initially the silylenes,…”

Section: Silylene Lewis Acid Complexesmentioning

confidence: 99%

Section: Silylene Lewis Acid Complexesmentioning

confidence: 99%

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Silylenes

Gaspar¹,

West²

2009

Patai's Chemistry of Functional Groups

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“…Such effects may be viewed as intramolecular blue shifts for the silylene n ~ p transition in the UV spectrum. Blue shifts have also been observed intermolecularly by the addition of Lewis bases (R20, R3N , R3P and R2S) as dopants to the organic solvent prior to formation of the glassy matrix and photolysis [22,23]. These spectral shifts are thought to indicate the partial occupation of the silylene p-type orbital by a lone pair of electrons from the Lewis base.…”

Section: R(trimethylsilyl)silylenes With Ama X < 600 Nmmentioning

confidence: 99%

The positions of λmax for some trimethylsilyl-substituted silylenes

Bott

Marshall

Wagenseller

et al. 1995

Journal of Organometallic Chemistry

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Low-temperature photolysis of tris(trimethylsilyl)silane derivatives in a 3-methylpentane glass at 77 K yields hexamethyldisilane and trimethylsilyl-substituted silylenes. These silylenes exhibit broad n ~ p absorptions at wavelengths typically > 600 nm in the UV and have been captured by 2,3-dimethylbutadiene in cyclohexane at room temperature. Exceptions to the usual position of Ama x have been observed and are discussed.

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Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

Lee

Sekiguchi

2010

Organometallic Compounds of Low‐Coordinate Si, Ge, Sn and Pb

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The Si-Si bonds of the oligo-or polysilanes chains can be cleaved upon photolysis in two ways, forming either silylenes or silyl radicals. 2 Thus, photolysis of both poly(di-nbutylsilane) and poly(di-n-hexylsilane) with shorter wavelength light [248 nm (pulsed) or 254 nm (CW)] resulted in both extrusion of silylenes R 2 Si • • (R = n-butyl or n-hexyl) trapped with Et 3 SiH and homolytic Si-Si bond cleavage, whereas only polysilyl radicals were observed upon irradiation with longer wavelength light (λ > 300 nm). 3 Among the most frequently used precursors for the photochemical generation of silylenes are trisilanes RR Si(SiMe 3 ) 2 , which readily eliminate hexamethyldisilane Me 3 Si-SiMe 3 to form the corresponding silylenes RR Si • •. Thus, diphenylsilylene Ph 2 Si • • was produced by irradiation of Ph 2 Si(SiMe 3 ) 2 along with the by-products formed from the isomeric silatriene (Scheme 4.1). 4

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The first spectroscopic detection of silaylides in the reaction of dimesitylsilylene with phosphorus, sulfur, and nitrogen-containing substrates. The stability of silaylides

Cited by 59 publications

References 4 publications

Silylenes

Silylenes

The positions of λmax for some trimethylsilyl-substituted silylenes

Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes

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