%0 Journal Article
%A Feng, Xiaojing
%A Maurya, Devendra S.
%A Bensabeh, Nabil
%A Moreno, Adrian
%A Oh, Takahiro
%A Luo, Yuqing
%A Lejnieks, Ja̅nis
%A Galià, Marina
%A Miura, Yoshiko
%A Monteiro, Michael J.
%A Lligadas, Gerard
%A Percec, Virgil
%D 2019
%T Replacing Cu(II)Br2 with Me6‑TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the
Mixed-Ligand Effect
%U 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
%R 10.1021/acs.biomac.9b01282.s001
%2 https://acs.figshare.com/ndownloader/files/17970437
%K monomer conversion
%K TREN
%K mixed-ligand system
%K DMF
%K mixed-ligand effect
%K MALDI-TOF
%K Mixed-Ligand Effect
%K chain end analysis studies
%K MA
%K SET-LRP
%K Statistical analysis
%K methyl acrylate
%K weight control
%K H 2 O
%K electron transfer-living
%K NMR
%K Cu
%K dipolar aprotic solvents NMP
%K tris
%K control experiments
%X 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.
%I ACS Publications