Copper(I) polyamine complexes have emerged as excellent atom-transfer radical polymerization catalysts. The rate of their reaction with organic halide initiators (the so-called activation step) varies across a broad range, depending on both the structure of the copper complex and the initiator. Herein, we report a new technique for determining the rate of copper-catalyzed activation (k(act)) using cyclic voltammetry coupled with electrochemical simulation. This method is applied to measuring k(act) for one of the most active catalysts, [Cu(I)(Me(6)tren)](+) (Me(6)tren = N,N,N-tris-(2-(dimethylamino)ethyl)amine), in reaction with ethyl bromoisobutyrate.
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