Abstract
Rate constants for the homolysis of aryl- substituted α-cumyl tert-butyl peroxides (X-PhCMe 2OOCMe 3) produce a Hammett plot with a ρ value of −0.22±.04. Both steric and electronic parameters influence the decomposition rate constants of tertiary alkyl peroxides with bulky substituents: log k rel = (−0.40±08)Σσ* −(0.43±.02)ΣE c s.
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