Rate Constants and Arrhenius Parameters for the Reactions of Some Carbon-Centered Radicals with Tris(trimethylsilyl)silane

Article abstract of DOI:10.1021/jo00022a035

Rate constants for the reactions of some carbon-centered radicals with (Me3Si)3SiH have been measured over a range of temperatures by using competing unimolecular radical reactions as timing devices.For example, the rate constants (at 298 K) are 3.7, 1.4, and 2.6 x 1E5 M^-1 s^-1 from primary, secondary, and tertiary alkyl radicals, respectively.Comparison of the radical trapping abilities of tri-n-butylstannane and tris(trimethylsilyl)silane is discussed.The use of 1,1-dimethyl-5-hexenyl cyclization as a radical clock has been recalibrated by using new data and data from the literature.