Ultraviolet photolysis of 1,2-Dimethyldisilane in the gas phase
The formation of MeSiH is the primary process in the photolysis of 1,2-dimethyldisilane at 193 nm that are analogues of carbenes. Gas chromatographic technique was used with a flame ionization detector as an analysis tool to identify the products mixture. The photolysis light at 193 nm was provided by an Oxford KX2 pulsed laser operated with rare-gas halide (known as an excimer laser) as the gain medium to provide ultraviolet (UV) radiation. This work has confirmed that radical processes are not important in the photolysis of 1,2-dimethyldisilane. A method for the determination of rate constants for MeSiH reactions relative to the rate constants of 1,2-dimethyldisilane has been formulated. This has been used to determine some relative rate constants of MeSiH insertions with methylsilanes. The insertion reactions of MeSiH with SiH4 and Methysilanes have shown to be fast and closer in reactivity to SiH2 than to SiMe2, whereas PhSiH looks to be slightly more reactive than MeSiH.
Reactions of silicon atoms with methane and silane in solid argon: A matrix-spectroscopic study
The reaction of silicon atoms with methane (1) and silane (7) in argon at 10 K has been studied. Methane (1) is found to be inert to silicon atoms, but reaction occurs upon photochemical excitation under formation of methylsilylene (2). On the contrary, silane (7) is spontaneously converted into a mixture of silylsilylene (10) and disilene (12). Subsequent irradiation generates the butterfly-type disilyne Si2H2 (14), together with a third photoproduct, which we assume to be the doubly bridged Si2H4 isomer 13. The structural elucidation of the new species is based on the comparison of the experimental IR and UV/Vis spectra with data from density functional theory calculations. The results are supported by isotopic labeling studies.
Maier, Guenther,Reisenauer, Hans Peter,Glatthaar, Joerg
By means of a combination of vacuum flash pyrolysis and matrix isolation silaethene (1a) and its simply substituted derivatives 1b-f can be prepared starting with precursors 9a-f of the silabicyclooctadiene type.Silaolefins 1a-f are stable in argon at 10 K and can be identified by their characteristic IR and UV spectra.
Maier, Guenther,Mihm, Gerhard,Reisenauer, Hans Peter
p. 2351 - 2368
(2007/10/02)
Hetero-?-Systems, 9. About the Relationships between Silaethenes and Methylsilylenes
Silaethenes 1 and the isomeric methylsilylenes 2 are separately existing species, but can readily be interconverted in an argon matrix via a photochemically induced 1,2-H shift.In case of the thermal excitation in the gas phase examples for both directions have been dedected spectroscopically: the isomerisation of a silaolefin into the corresponding silylene (1d -> 2d) and the formation of a silene from a silylene (2f -> 1f).
Maier, Guenther,Mihm, Gerhard,Reisenauer, Hans Peter,Littmann, Dieter
p. 2369 - 2381
(2007/10/02)
Reversible Photoisomerisierung zwischen Silaethenen und Methylsilylenen (Methylsilandiylen)
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Reisenauer, Hans Peter,Mihm, Gerhard,Maier, Guenther
p. 864 - 865
(2007/10/02)
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