Abstract Absolute rate constants for the addition of the 2-cyano-2-propyl radical to 26 alkenes CH 2= CXY at 315 K were determined in solution by time-resolved electron-spin- resonance spectroscopy. They vary with the alkene substituents from 30 M− 1 s− 1 to 7′ 010 M− 1 s− 1. For styrene the temperature dependence is given by log k/M− 1 s− 1= 7.7− 26.1/Θ where Θ= 2.303 RT in kJ/mol. An analysis of the substituent effects in terms of polar ...
