Rare earth metal bisamido complexes with an NNO tridentate ligand and catalytic activity for the selective polymerization of isoprene
Rare earth metal bisamido complexes with an NNO tridentate ligand and catalytic activity for the selective polymerization of isoprene
复制标题
具有NNO三齿配体的稀土金属双酰胺配合物及其对异戊二烯选择性聚合的催化活性
DOI：
10.1039/c7nj01454f
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发表时间：
2017
影响因子：
3.3
通讯作者：
Mu Xiaolong
中科院分区：
文献类型：
--
作者：
Gu Xiaoxia;Wang Shaowu;Wei Yun;Zhu Xiancui;Zhou Shuangliu;Huang Zeming;Mu Xiaolong
将4-（（2-（吡啶-2-基）乙基）亚氨基）辛-2-烯-2-醇（HL，1）与1当量的四氢呋喃（THF）在室温下反应。[（Me_3Si）_2N]_3RE（μ-Cl）Li（THF）_3与吡啶基β-酮亚胺NNO三齿配体[LRE{[N（SiMe_3）_2]_2}]（L = CH_3C（O）CHC（CH_3）NCH_2CH_2（2-C_5H_4N），RE = Y（2），Nd（3），Sm（4），Gd（5），Dy（6），Er（7）和Yb（8）形成稀土金属双酰胺配合物.所有配合物通过元素分析和光谱分析进行了充分的表征，并通过单晶X-射线衍射研究进一步确定其结构。此外，研究了配合物2-8作为异戊二烯聚合的预催化剂。结果表明，除配合物4和配合物8外，所有配合物在助催化剂存在下均能有效引发异戊二烯聚合，得到高区域和立体选择性的聚异戊二烯（1，4-顺式选择性高达97.1%）。
The reaction of 4-((2-(pyridin-2-yl)ethyl)imino)pent-2-en-2-ol (HL, 1) with 1 equiv. of [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produces rare earth metal bisamido complexes incorporating the pyridyl-functionalized β-ketoiminato NNO tridentate ligand [LRE{[N(SiMe3)2]2}] (L = CH3C(O)CHC(CH3)NCH2CH2(2-C5H4N), RE = Y (2), Nd (3), Sm (4), Gd (5), Dy (6), Er (7) and Yb (8)). All the complexes were fully characterized via elemental and spectroscopic analyses, and their structures were further determined via single-crystal X-ray diffraction study. Additionally, complexes 2–8 were investigated as precatalysts for isoprene polymerization. The results showed that except for complexes 4 and 8, all the complexes could effectively initiate the polymerization of isoprene to afford polyisoprene with high regio- and stereo-selectivity (1,4-cis selectivity up to 97.1%) in the presence of cocatalysts.