Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 2705 - 2712 (1983)
Update date:2022-08-28
Topics:
Chandra, Harish
Davidson, Iain M. T.
Symons, Martyn C. R.
The aim of this study was to probe the utility of the spin-trapping tecnique for the identification and estimation of radicals derived from organosilicon compounds in the gas phase.The methods of generation comprised electric discharge and mercury-senzitized photolysis; the traps were Me3C-NO and PhCN=N(O)CMe3.After establishing that the procedures were satisfactory, using toluene and n-hexane as radical sources, a range of monosilanes was studied.Several systems gave reasonable yields of spin-trap radicals.For example, SiMe4 gave H2C.SiMe3 adducts, Me3SiH gave H2C.Si(H)Me3 and Me3Si. adducts and PhSiH3 gave PhSiH2 adducts.Certain chlorosilanes gave chlorine atom adducts using electric-discharge generation, but only very weak signals from unknown radical derivatives using the photolytic method.In many other cases, such as Me2SiH2 and MeSiH3, we were unable to detect any radical products despite extensive attempts under a wide range of conditions.We conclude that the technique is quite satisfactory for the detection of carbon-centred radicals, but is less reliable for the study of silyl radicals.In a few cases, we also used 2,6-di-t-butylquinone as a trap, but the results were less satisfactory than with the nitrone trap.
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