Synthesis, Characterization, and Catalytic Activity of Dinuclear Rare-Earth Metal Alkyl Complexes Bearing 2,6-Diisopropylphenylamidomethyl Functionalized Pyrrolyl Ligand
Synthesis, Characterization, and Catalytic Activity of Dinuclear Rare-Earth Metal Alkyl Complexes Bearing 2,6-Diisopropylphenylamidomethyl Functionalized Pyrrolyl Ligand
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带有 2,6-二异丙基苯基酰胺甲基官能化吡咯基配体的双核稀土金属烷基配合物的合成、表征和催化活性
DOI：
10.1021/acs.organomet.1c00097
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发表时间：
2021-06
期刊：
影响因子：
2.8
通讯作者：
Wang Shaowu
中科院分区：
文献类型：
--
作者：
Zhu Xiancui;Guo Dianjun;Yao Fangshi;Huang Zeming;Li Yang;Xie Zuowei;Wang Shaowu
通过稀土三烷基络合物RE(CH2SiMe3)3RE(μ-L)2RE(THF)2(L=2-(2，6-iPr2C6H3NCH2)C4H3N；RE=Y(1a)，Gd(2a)，Dy(3a)，Er(4a)，Yb(5a)，Lu(6a)，THF=四氢呋喃)与2-(2，6-iPr2C6H3NCH2)C4H3N，RE(CH2SiMe3)3(THF)2在甲苯中的反应，在室温下合成了一系列结构明确的阳离子稀土金属桥联吡咯稀土双烷基络合物。当反应温度提高到45℃时，以较好的产率得到了中心对称的半夹心型吡咯基稀土金属烷基配合物(Me_3SiCH_2RELthf)_2(RE=Y(1b)，Gd(2b)，Yb(5b))。进一步的研究发现，通过将C6D6溶液加热到60℃，夹心吡咯基稀土金属二烷基配合物可以转移到半夹心稀土金属异构体上。单晶X射线衍射分析表明，夹心吡咯基稀土金属二烷基是由一个八面体阳离子稀土金属桥联而成的，这个八面体阳离子稀土金属是由四氢呋喃分子中的两个N原子、两个N原子和两个O原子配位的；而在它们的异构体中，稀土金属被一个吡咯烷基配体、一个烷基、一个四氢呋喃分子和一个η5型的吡咯环所包围。用光谱分析、元素分析和单晶X-射线分析对所有配合物进行了表征。结果表明，在助催化剂存在下，双核稀土烷基配合物对异戊二烯聚合表现出高活性和高的区域选择性和立体选择性，顺-1，4-基团的选择性高达96.6%。
A series of structurally well-defined cationic rare-earth metal bridged sandwich pyrrolyl rare-earth metal dialkyl complexes with the general formula of (Me3SiCH2)2RE(μ-L)2RE(thf)2(L= 2-(2,6-iPr2C6H3NCH2)C4H3N; RE = Y (1a), Gd (2a), Dy (3a), Er (4a), Yb (5a), Lu (6a), thf = tetrahydrofuran) were synthesized by the reactions of rare-earth metal trialkyl complexes RE(CH2SiMe3)3(thf)2with 1 equiv of 2-(2,6-diisopropylphenylaminomethyl)pyrrole (H2L) in toluene at room temperature. When the reaction temperature was raised to 45 °C, the centrosymmetric half-sandwich pyrrolyl rare-earth metal alkyl complexes (Me3SiCH2RELthf)2(RE = Y (1b), Gd (2b), Yb (5b)) were obtained in good yields, unexpectedly. Further studies revealed that the sandwich pyrrolyl rare-earth metal dialkyl complexes can be transferred to the half-sandwich rare-earth metal isomers by heating the C6D6solution to 60 °C. Single-crystal X-ray diffraction analyses revealed that the sandwich pyrrolyl rare-earth metal dialkyls were bridged by an octahedral cationic rare-earth metal coordinated by two N atoms of the pyrrolyl rings, two N atoms of the amido moieties, and two O atoms of the thf molecules; while in their isomers, the rare-earth metals were surrounded by a pyrrolyl ligand, an alkyl group, a molecule of thf, and an η5type of pyrrolyl ring. All complexes were characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray analyses. Moreover, the catalytic behaviors of these complexes were investigated, and the results showed that, in the presence of cocatalysts, the dinuclear rare-earth metal alkyl complexes exhibited high activities and high regio- and stereoselectivities for isoprene polymerization withcis-1,4-units up to 96.6%.
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影响因子：
2.8
作者：
Kuburat O Saliu;Jianhua Cheng;R. McDonald;Michael J. Ferguson;J. Takats
通讯作者：
Kuburat O Saliu;Jianhua Cheng;R. McDonald;Michael J. Ferguson;J. Takats
DOI：
10.1107/s2053229614024929
发表时间：
2015-01-01
影响因子：
0.8
作者：
Spek, Anthony L.
通讯作者：
Spek, Anthony L.
影响因子：
--
作者：
Hongbo Li;Liting Li;T. Marks
通讯作者：
Hongbo Li;Liting Li;T. Marks
影响因子：
--
作者：
Lixin Zhang;M. Nishiura;M. Yuki;Yi Luo;Z. Hou
通讯作者：
Lixin Zhang;M. Nishiura;M. Yuki;Yi Luo;Z. Hou
带有受限几何构象配体的稀土金属烯丙基前体对异戊二烯的活性催化链增长聚合和嵌段共聚
影响因子：
4.9
作者：
Jian, Zhongbao;Cui, Dongmei;Li, Xiaofang
通讯作者：
Li, Xiaofang