Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization

The equilibrium of copper-catalyzed atom transfer radical polymerization was investigated in silico with the aim of finding an explanation for the experimentally observed solvent effect. Various combinations of alkyl halide initiators and copper complexes in acetonitrile (MeCN) and dimethyl sulfoxide (DMSO) were taken into consideration. A continuum model for solvation, which does not account for the explicit interactions between the solvent and metal complex, is not adequate and does not allow the reproduction of the experimental trend. However, when the solvent molecules are included in the coordination sphere of the copper(I,II) species and the continuum description of the medium is still used, a solvent dependence of process thermodynamics emerges, in fair agreement with experimental trends.