Rate constants for the addition of the 2-hydroxy-2-propyl radical to alkenes in solution |
| |
Authors: | K Hberger H Fischer |
| |
Institution: | K. Héberger,H. Fischer |
| |
Abstract: | Absolute rate constants for the addition of the 2-hydroxy-2-propyl radical to 18 substituted alkenes (CH2 = CXY) were determined at (296 ± 1) K in 2-propanol by time-resolved electronspin-resonance spectroscopy. With alkene substitution the rate constants vary by more than 6 orders of magnitude. For 3,3-dimethyl-but-1-ene the temperature dependence is given by log k/M?1 · s?1 = 6.4 minus;; 19.1/Θ where Θ = 2.303 RT in kJ/mol?1. As shown by a good correlation with the alkene electron affinities, log k296/M?1 · s?1 = 6.46 + 1.71 · EA/eV (r = 0.930), 2-hydroxy-2-propyl is a very nucleophilic radical, and its addition rates are highly governed by polar effects. © 1993 John Wiley & Sons, Inc. |
| |
Keywords: | |
|
|