Synthesis,Characterization of Rare-Earth Metal Chlorides Bearing Indolyl-Based NCN Pincer Ligand and Their Catalytic Activity toward 1,4-cis Polymerization of Isoprene  

作　　者：Zeming Huang Shaowu Wang Xiancui Zhu Yun Wei Qingbing Yuan Shuangliu Zhou Xiaolong Mu Hua Wang 

机构地区：[1]Key Laboratory of Functional Molecular Solids,Ministry of Education,Anhui Laboratory of Molecule-Based Materials,College of Chemistry and Materials Science,Anhui Normal University,Wuhu,Anhui 241000,China [2]Anhui Laboratory of Clean Catalytic Engineering,Anhui Laboratory of Functional Coordinated Complexes for Materials Chemistry and Application,College of Chemical and Environmental Engineering,Anhui Polytechnic University,Wuhu,Anhui 241000,China [3]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Chinese Journal of Chemistry》2021年第12期3360-3368,共9页中国化学（英文版）

基　　金：Financial support for this work was provided by the National Natural Science Foundation of China(Nos.21432001,21871004,21861162009);the grants from Anhui Province(2017D107).

摘　　要：A novel indolyl-based NCN pincer ligand precursor HL(HL=(1-(2-(CH_(2))_(4)NCH_(2)CH_(2))-3-(2,6-ipr_(2)C_(6)H_(3)N=CH)C_(8)H_(5)N))was rationally and precisely designed,and successfully prepared in a high yield.Lithiation of HL with ^(n)BuLi in n-hexane,followed by treatment with RECl_(3) in THF led to the isolation of rare-earth metal chlorides in monomeric form(κ^(3)-L)RECI_(2)(THF)(RE=Sc(2),Yb(3)),and dimeric form[(κ^(3)-L)RECI(THF)(μ-Cl)]_(2)(RE=Er(4),Y(5))bearing the novel indolyl-based NCN pincer ligand in designed pincer ligation depending on different metal ionic radii;and the chloride bridged rare-earth metal and lithium mixed complexes in form(κ^(2)-L)_(2)RE(μ-Cl)_(2)Li(THF)_(2)(RE=Y(6),Dy(7)).All complexes were fully characterized and their structures were determined.The diamagnetic complexes 2,5 and 6 were furtherly characterized by the NMR spectroscopic method.The catalytic activity studies revealed that the central metal ions,borates,aluminum alkyls,and ligation of the central metal ions have influences on catalytic activity,and regio-and stereoselectivity for the polymerization of isoprene.With cooperation of the cocatalysts,the pincer-type yttrium chloride 5 initiated the isoprene polymerization with a high activity producing polymers with high regio-and stereoselectivity(1,4-cis polymers up to 99.6%),and the Mn as high as 8.76×10^(5).

关 键 词：Rare earth Pincer-ligand Indolyl POLYMERIZATION SELECTIVITY 

分 类 号：O641.4[理学—物理化学]