Gas phase kinetic study of the thermal reactions of t‐butoxy radicals with germane, phosphine, and trimethylsilane

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