Me 6 -TREN/TREN Mixed-Ligand Effect During SET-LRP in the Catalytically Active DMSO Revitalizes TREN into an Excellent Ligand
Me 6 -TREN/TREN Mixed-Ligand Effect During SET-LRP in the Catalytically Active DMSO Revitalizes TREN into an Excellent Ligand
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Me 6 -TREN/TREN 混合配体效应在催化活性 DMSO 中的 SET-LRP 过程中使 TREN 重新成为优秀的配体
DOI：
10.1021/acs.biomac.9b01765
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发表时间：
2020
影响因子：
6.2
通讯作者：
Percec, Virgil
中科院分区：
文献类型：
--
作者：
Maurya, Devendra S.;Malik, Ayesha;Feng, Xiaojing;Bensabeh, Nabil;Lligadas, Gerard;Percec, Virgil
用Cu(0)线催化双（2-溴丙基）乙烷（BPE）引发的丙烯酸甲酯（MA）在DMSO中聚合（SET-LRP）时，发现三（2-二甲氨基乙基）胺（Me6-TREN）与三（2-氨基乙基）胺（TREN）配体的混合物存在混合配体效应。SET-LRP在Me6-TREN、TREN和混合配体Me6-TREN/TREN存在时，在DMSO中的外反应顺序与在Cu(0)粉末存在时的催化活性相似。DMSO的催化活性，具有接近100%的链端功能，使得价格便宜得多的TREN作为一种非常有效的配体，与Me6-TREN和混合配体竞争，并使TREN重新成为一种优秀的配体。配体之间以1/1的比例混合配体的最高活性表明，除了两种配体之间的快速交换外，一种新的由氢键稳定的单一动态配体可能产生这些结果。
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.