Gas Phase Kinetic Study of the Thermal Reactions of t-Butoxy Radicals with Germane, Phosphine, and Trimethylsilane
1986
The hydrogen abstraction reactions of tert-butoxyl with germane, phosphine, and trimethylsilane were studied by pyrolyzing di-t-butyl peroxide in the temperature range of 403 to 458 K. From the reported rate constant for the tert-butoxy radical decomposition in the literature, the absolute rate constants were determined from the study of competitive reaction between t-butoxy radical decomposition
and hydrogen abstraction reaction. (t-BuO + RH → t-BuOH + R, where RH = GeH4, PH3, and HSiMe3)
The Arrhenius parameters are found to be as follows: Text
Table Text. Ea(kcal mol−1) Log A(1.mol−1s−1)
t-BuO + SiHMe3 2.1 8.5
t-BuO + GeH4 1.9 9.1
t-BuO + PH3 1.4 9.0
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