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The rate coefficients for activation (k_a0^app) of two alkyl halides, methyl 2-bromopropionate, MBrP, and Br-capped poly(methyl acrylate), by Cu⁰ were determined under various conditions. The value of k_a0^app was studied in two solvents, dimethyl sulfoxide (DMSO) and acetonitrile (MeCN), and their mixtures with methyl acrylate (MA), using tris[2-(dimethylamino)ethyl]amine (Me₆TREN) and tris(2-pyridylmethyl)amine (TPMA) as ligands. The experiments showed that the rate of activation increased with the surface area of Cu⁰ but was typically not affected by the ratio of ligand to initiator, if a sufficient amount of ligand was present. The choice of solvent and presence of monomer/polymer had a small influence on k_a0^app. The activation rate coefficient of MBrP was k_a0^app= 1.8 × 10^–4 cm s^–1 with Me₆TREN as the ligand in DMSO at 25 °C while the activation rate coefficient of Br-capped poly(methyl acrylate) by Cu⁰ …