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.
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