Replacing Cu(II)Br₂ with Me₆‑TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect

The mixed-ligand system consisting of tris­(2-aminoethyl)­amine (TREN) and tris­(2-dimethylaminoethyl)­amine (Me₆-TREN) during the Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) in “programmed” biphasic mixtures of the dipolar aprotic solvents NMP, DMF, and DMAc with H₂O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo “click” reaction demonstrated that Me₆-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu­(II)­Br₂. Statistical analysis of the kinetic data together with control experiments demonstrated that this mixed-ligand effect enhanced the apparent rate constant of propagation, monomer conversion, and molecular weight control. The most efficient effect was observed at a 1/1 molar ratio between these two ligands, suggesting that in addition to a fast exchange between the two ligands, a new single dynamic ligand generated by hydrogen bonding may be responsible for the mixed ligand observed.