title: New method for exploring deactivation kinetics in copper-catalyzed atom-transfer-radical reactions.
abstract: Copper polyamine complexes are among the most utilized catalysts for controlled radical polymerization reactions. Copper(I) complexes may react reversibly with an alkyl halide to form an alkyl radical, which promotes polymerization, and a copper(II) halido complex in a step known as activation. The kinetics of the reverse reaction between the alkyl radical and higher oxidation-state copper complex (deactivation) are less studied because these reactions approach diffusion-controlled rates, and it is difficult to isolate or quantify the concentration of the alkyl radical (R(•)) in situ. Herein we report a broadly applicable electrochemical technique for simultaneously measuring the kinetics of deactivation and kinetics of activation.
authors.affiliation: School of Chemistry and Molecular Biosciences, University of Queensland , Brisbane 4072, Australia.
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Zerk
authors.forename: Paul V
authors.initials: PV
authors.lastname: Bernhardt