Rate constants for the reaction of cumylperoxyl radicals with group 14 hydrides

Abstract

Rate constants for the reaction of a cumylperoxyl radical with a variety of group 14 hydrides were measured by using inhibited hydrocarbon oxidation methodologies. In the silane series the rate constants at 345.5 K are in the range 0.10–0.90 M⁻¹ s⁻¹ for t-BuSiHMe₂, PhSiH₃, PhSiHMe₂, Ph₂SiH₂, Ph₂SiHMe and Ph₃SiH, whereas the rate constant for (TMS)₃SiH is 2–3 orders of magnitude higher. The rate constants for Bu₃GeH and Bu₃SnH are 19.4 and 1.8 × 10³ M⁻¹ s⁻¹, respectively, at 345.5 K. The trends in reactivity for these reactions are similar to those observed for other radicals with group 14 hydrides although the reactions are several orders of magnitude slower.