Copper complexes of tertiary amine ligands have emerged as the catalysts of choice in the extensively employed atom transfer radical polymerization (ATRP) protocol. The halide ligand substitution reactions of five-coordinate copper(II) complexes of tris[2-(dimethylamino)ethyl]amine (Me(6)tren), one of the most active ATRP catalysts, has been studied in a range of organic solvents using stopped-flow techniques. The kinetic and activation parameters indicate that substitution reactions on [Cu-II(Me(6)tren)X](+) (X- = Cl- and Br-) and [Cu-II(Me(6)tren)(Solv)](2+) (Solv = MeCN, DMF, DMSO, MeOH, EtOH) are dissociatively activated; this behavior is independent of the solvent used. Adjusting the effective concentration of the solvent by addition of an olefinic monomer to the solution does not affect the kinetics of the halide binding (k(on)) but can alter the outer-sphere association equilibrium constant (K-OS) between reactants prior to the formal ligand substitution. Halide (X-/Y-) exchange reactions (X = Br and Y = Cl) involving the complex [Cu(Me(6)tren)X](+) and Y- reveal that the substitution is thermodynamically favored. The influence of solvent on the substitution reactions of [Cu(Me(6)tren)X](+) is complex; the more polar DMF confers a greater entropic driving force but larger enthalpic demands than MeCN., These substitution reactions are compared with those for copper(II) complexes bearing the tris[2-(diethylamino)ethyl]amine (Et(6)tren) and tris[2-(pyridyl)methyl] amine (tpa) ligands, which have also been used as catalysts for ATRP. Changing the ligand has a significant impact on the kinetics of X-/Y- exchange. These correlations are discussed in relation to the ability of five-coordinate [CuLX](+) complexes to deactivate radicals in ATRP.