Replacing Cu(II)Br<sub>2</sub> with Me<sub>6</sub>‑TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect Xiaojing Feng Devendra S. Maurya Nabil Bensabeh Adrian Moreno Takahiro Oh Yuqing Luo Ja̅nis Lejnieks Marina Galià Yoshiko Miura Michael J. Monteiro Gerard Lligadas Virgil Percec 10.1021/acs.biomac.9b01282.s001 https://acs.figshare.com/articles/journal_contribution/Replacing_Cu_II_Br_sub_2_sub_with_Me_sub_6_sub_TREN_in_Biphasic_Cu_0_TREN_Catalyzed_SET-LRP_Reveals_the_Mixed-Ligand_Effect/9971375 The mixed-ligand system consisting of tris­(2-aminoethyl)­amine (TREN) and tris­(2-dimethylaminoethyl)­amine (Me<sub>6</sub>-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 H<sub>2</sub>O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo “click” reaction demonstrated that Me<sub>6</sub>-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu­(II)­Br<sub>2</sub>. 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. 2019-10-11 14:49:51 monomer conversion TREN mixed-ligand system DMF mixed-ligand effect MALDI-TOF Mixed-Ligand Effect chain end analysis studies MA SET-LRP Statistical analysis methyl acrylate weight control H 2 O electron transfer-living NMR Cu dipolar aprotic solvents NMP tris control experiments