Me6-TREN/TREN Mixed-Ligand Effect During SET-LRP in the Catalytically Active DMSO Revitalizes TREN into an Excellent Ligand.,Biomacromolecules

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Me6-TREN/TREN Mixed-Ligand Effect During SET-LRP in the Catalytically Active DMSO Revitalizes TREN into an Excellent Ligand.
Biomacromolecules ( IF 5.5 ) Pub Date : 2020-02-07 , DOI: 10.1021/acs.biomac.9b01765
Devendra S Maurya ₁ , Ayesha Malik ₁ , Xiaojing Feng _{1,

2} , Nabil Bensabeh ₃ , Gerard Lligadas _{1,

3} , Virgil Percec ₁

Affiliation

A mixed-ligand effect was observed for mixtures of tris(2-dimethylaminoethyl)amine (Me6-TREN) with tris(2-aminoethyl)amine (TREN) ligands during Cu(0) wire-catalyzed, single-electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) initiated with bis(2-bromopropionyl)ethane (BPE) in DMSO. The external order of reaction of SET-LRP both in the presence of Me6-TREN, TREN and of the mixed-ligand Me6-TREN/TREN, in DMSO, demonstrated a catalytic activity for DMSO similar to that reported in the presence of Cu(0) powder. The catalytic activity of DMSO, with close to 100% chain-end functionality, facilitates the much less expensive TREN to act as a very efficient ligand that is competitive with Me6-TREN and with the mixed-ligand and revitalizes TREN into an excellent ligand. The highest activity of the mixed-ligand at 1/1 ratio between ligands suggests that in addition to a fast exchange between these two ligands, a new single dynamic ligand stabilized by hydrogen-bonding, may generate these results.

中文翻译：

催化活性DMSO中SET-LRP期间的Me6-TREN / TREN混合配体效应可将TREN活化为出色的配体。

在铜（0）线催化的单电子转移活性基团中，观察到三（2-二甲基氨基乙基）胺（Me6-TREN）与三（2-氨基乙基）胺（TREN）配体的混合物的混合配体效应双（2-溴丙酰基）乙烷（BPE）在DMSO中引发的丙烯酸甲酯（MA）聚合反应（SET-LRP）。在DMSO中，在Me6-TREN，TREN和混合配体Me6-TREN / TREN存在下，SET-LRP的外部反应顺序证明了对DMSO的催化活性类似于在Cu（ 0）粉末。DMSO具有接近100％的链端官能度，具有催化活性，它使便宜得多的TREN成为非常有效的配体，可与Me6-TREN和混合配体竞争，并将TREN活化为出色的配体。

更新日期：2020-01-28

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