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

Rate constants for the reaction of a cumylperoxyl radical with a variety of group 14 hydrides were measured by using inhibited hydrocarbon oxidation m ethodologies. 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, Ph2Si HMe and Ph3SiH, whereas the rate constant for (TMS)(3)SiH is 2-3 orders of magnitude higher. The rate constants for Bu3GeH and Bu3SnH are 19.4 and 1.8 x10(3) M-1 s(-1), respectively, at 345.5 K. The trends in reactivity for th ese reactions are similar to those observed for other radicals with group 1 4 hydrides although the reactions are several orders of magnitude slower.