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

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Chinese Journal of Chemistry 2021年第12期39卷 3360-3368页

作者： Zeming Huang Shaowu Wang Xiancui Zhu Yun Wei Qingbing Yuan Shuangliu Zhou Xiaolong Mu Hua Wang Key Laboratory of Functional Molecular Solids Ministry of EducationAnhui Laboratory of Molecule-Based MaterialsCollege of Chemistry and Materials ScienceAnhui Normal UniversityWuhuAnhui 241000China Anhui Laboratory of Clean Catalytic Engineering Anhui Laboratory of Functional Coordinated Complexes for Materials Chemistry and ApplicationCollege of Chemical and Environmental EngineeringAnhui Polytechnic UniversityWuhuAnhui 241000China State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China

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 *** 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 *** diamagnetic complexes 2,5 and 6 were furtherly characterized by the NMR spectroscopic *** 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 *** 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

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