Résumé | The absolute rate constants for the reactions of n-Bu 3Ge· and n-Bu 3Sn· radicals with a wide variety of organic compounds have been measured in solution at ca. 300 K by using laser flash photolysis techniques. For most of the substrates examined the n-Bu 3Ge· and n-Bu 3Sn· radicals were found to have essentially equal reactivity, e.g., the measured rate constants were 7.4 × 10 8 and 1.4 × 10 9 M -1 s -1, respectively, for duroquinone; 9.6 × 10 7 and 1.3 × 10 8 M -1 s -1, respectively, for benzil; 8.6 × 10 7 and 9.9 × 10 7 M -1 s -1, respectively, for styrene; 4.6 × 10 7 and 6.8 × 10 -1 M -1 s -1, respectively, for 1,4-pentadiene; and 8.6 × 10 7 and 1.7 × 10 8 M -1 s -1, respectively, for tert-butyl bromide. In all their reactions, these two radicals are less reactive than triethylsilyl radicals. From literature data we are able to estimate that the inversion of triorganogermyl radicals is somewhat slower than that for triorganosilyl radicals. Published 1984 by the American Chemical Society. |
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