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Synthesis, structure and catalytic activity of rare-earth metal amino complexes incorporating imino-functionalized indolyl ligand
Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2020-12-20 , DOI: 10.1016/j.jorganchem.2020.121661
Lu Yu , Fenhua Wang , Hui Wang , Shaoyin Wang , Yunjun Wu , Xiaoxia Gu

The reactions of the imino-functionalized indolyl ligand (HL, L = 3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5N) with the rare-earth metal amides [(Me3Si)2N]3RE(µ-Cl)Li(THF)3 producing different types of rare-earth metal amido complexes were investigated. The reactions of HL with 1 equiv. of [(Me3Si)2N]3RE(µ-Cl)Li(THF)3 generated a series of hetero-nuclear bimetallic rare-earth metal amino complexes {[η1:µ-η2-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5]RE[N(SiMe3)2]2(µ-Cl)Li(THF)} (RE = Y(1), Sm(2), Gd(3), Er(4), Yb(5)). By extending the reaction time, only the reaction of HL with [(Me3Si)2N]3Gd(µ-Cl)Li(THF)3 gave an unexpected binuclear rare-earth metal complex {[(µ-η5:η1):η1:η1-3-[(Me2N)2-C14H9]-(NCH2CH2-C8H5N)2]Gd2[N(SiMe3)2]3} (6) incorporating a novel polycyclic ligand through C-C and C-N coupling. Treatment of HL with [(Me3Si)2N]3Sm(µ-Cl)Li(THF)3 in a 2:1 ratio generated the bis(indolyl) heteronuclear bimetallic rare-earth metal amino complex {(η1:η1-[µ-η2:η1-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5]Li[µ-η2:η1-3-(4-Me2N-C6H4CH=N-CH2CH2)C8H5])Sm[N(SiMe3)2]2} (7) in low yield probably due to accompanying with the formation of the complex 2. The above results indicated that reaction conditions play important roles in the formation of different coordination modes of the imino-functionalized indolyl rare-earth metal amido complexes. All new complexes 17 are fully characterized including X-ray structural determination. The catalytic activity of complexes 1-7 for the addition of amines to carbodiimides was explored. The results showed that all complexes displayed an excellent activity towards the addition of amines to carbodiimides producing guanidine under solvent-free condition.



中文翻译:

含亚氨基官能化吲哚基配体的稀土金属氨基配合物的合成,结构和催化活性

亚氨基官能化的吲哚基配体(H L,L  = 3-(4-Me 2 N-C 6 H 4 CH = N-CH 2 CH 2)C 8 H 5 N)与稀土金属酰胺的反应[(研究了产生不同类型稀土金属酰胺配合物的Me 3 Si)2 N] 3 RE(µ -Cl)Li(THF)3。H L与1当量的反应。[(Me 3 Si)2 N] 3 RE(µ -Cl)Li(THF)3的原子数产生了一系列的异核双金属稀土类金属的氨基络合物{[ η 1μ - η 2 -3-(4-我2 N-C 6 H ^ 4 CH = N-CH 2 CH 2)C 8 H ^ 5 ] RE [N(SiMe 32 ] 2μ- Cl)Li(THF)}(RE = Y(1),Sm(2),Gd(3),Er(4),Yb(5))。通过延长反应时间,仅H L与[(Me 3 Si)2 N] 3的Gd(μ -Cl)的Li(THF)3,得到意想不到的双核稀土类金属络合物{[(μ - η 5η 1):η 1η 1 -3 - [(ME 2 N)2 -C 14 H 9 ]-(NCH 2 CH 2 -C 8 H 5 N)2 ] Gd 2 [N(SiMe 32 ] 3 }(6)通过CC和CN偶联引入新型多环配体。H的治疗大号用[(ME 3 Si)的2 N] 3的Sm(μ -Cl)的Li(THF)3在一2:产生的二(吲哚基)异核双金属稀土类金属氨基1比复杂{(η 1η 1 - [ μ - η 2η 1 -3-(4-我2 N-C 6 H ^ 4 CH = N-CH 2 CH 2)C 8 H ^ 5 ]的Li [ μ - η 2η 1 -3-(4-我2 N-C 6 H ^ 4 CH = N-CH 2 CH 2)C 8 H ^ 5 ])的Sm [N(森达32 ] 2 }(7在低的产率)可能是由于与配合物的形成2。以上结果表明反应条件在亚氨基官能化的吲哚基稀土金属酰胺配合物的不同配位方式的形成中起重要作用。所有新复合物17具有X射线结构确定等特征。配合物的催化活性1 - 7用于添加胺碳化二亚胺进行了探讨。结果表明,在无溶剂条件下,所有配合物均表现出优异的活性,可将胺加到碳二亚胺中生成胍。

更新日期:2020-12-29
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