Peroxyl Radical Clocks
A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (kH-tocopherol = 3.5 × 106 M-1 s-1, kH-linoleate = 62 M-1 s-1). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 100 to 107 M-1 s-1.
Repository citation: Roschek, Bill; Tallman, Keri A.; Rector, Christopher L.; Gillmore, Jason G.; Pratt, Derek A.; Punta, Carlo; and Porter, Ned A., "Peroxyl Radical Clocks" (2006). Faculty Publications. Paper 1040.
Published in: Journal of Organic Chemistry, Volume 71, Issue 9, April 28, 2006, pages 3527-3532. Copyright © 2006 American Chemical Society, Washington, D.C..