Rare-Earth-Metal-Hydrocarbyl Complexes Bearing Linked Cyclopentadienyl or Fluorenyl Ligands: Synthesis, Catalyzed Styrene Polymerization, and Structure-Reactivity Relationship
文献类型：期刊论文
| 作者 | Jian, Zhongbao1,2; Cui, Dongmei1; Hou, Zhaomin3 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2012-02-01 |
| 卷号 | 18期号:9页码:2674-2684 |
| 关键词 | Cyclopentadienyl Ligands Hydrocarbyl Complexes Ligand Effects Polymerization Rare-earth Metals |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201102682 |
| 英文摘要 | A series of rare-earth-metalhydrocarbyl complexes bearing N-type functionalized cyclopentadienyl (Cp) and fluorenyl (Flu) ligands were facilely synthesized. Treatment of [Y(CH2SiMe3)3(thf)2] with equimolar amount of the electron-donating aminophenyl-Cp ligand C5Me4H-C6H4-o-NMe2 afforded the corresponding binuclear monoalkyl complex [({C5Me4-C6H4-o-NMe(mu-CH2)}Y{CH2SiMe3})2] (1?a) via alkyl abstraction and C?H activation of the NMe2 group. The lutetium bis(allyl) complex [(C5Me4-C6H4-o-NMe2)Lu(?3-C3H5)2] (2?b), which contained an electron-donating aminophenyl-Cp ligand, was isolated from the sequential metathesis reactions of LuCl3 with (C5Me4-C6H4-o-NMe2)Li (1 equiv) and C3H5MgCl (2 equiv). Following a similar procedure, the yttrium- and scandiumbis(allyl) complexes, [(C5Me4-C5H4N)Ln(?3-C3H5)2] (Ln=Y (3?a), Sc (3?b)), which also contained electron-withdrawing pyridyl-Cp ligands, were also obtained selectively. Deprotonation of the bulky pyridyl-Flu ligand (C13H9-C5H4N) by [Ln(CH2SiMe3)3(thf)2] generated the rare-earth-metaldialkyl complexes, [(?3-C13H8-C5H4N)Ln(CH2SiMe3)2(thf)] (Ln=Y (4?a), Sc (4?b), Lu (4?c)), in which an unusual asymmetric ?3-allyl bonding mode of Flu moiety was observed. Switching to the bidentate yttriumtrisalkyl complex [Y(CH2C6H4-o-NMe2)3], the same reaction conditions afforded the corresponding yttrium bis(aminobenzyl) complex [(?3-C13H8-C5H4N)Y(CH2C6H4-o-NMe2)2] (5). Complexes 15 were fully characterized by 1H and 13C NMR and X-ray spectroscopy, and by elemental analysis. In the presence of both [Ph3C][B(C6F5)4] and AliBu3, the electron-donating aminophenyl-Cp-based complexes 1 and 2 did not show any activity towards styrene polymerization. In striking contrast, upon activation with [Ph3C][B(C6F5)4] only, the electron-withdrawing pyridyl-Cp-based complexes 3, in particular scandium complex 3?b, exhibited outstanding activitiy to give perfectly syndiotactic (rrrr >99?%) polystyrene, whereas their bulky pyridyl-Flu analogues (4 and 5) in combination with [Ph3C][B(C6F5)4] and AliBu3 displayed much-lower activity to afford syndiotactic-enriched polystyrene. |
| 语种 | 英语 |
| WOS记录号 | WOS:000300691000030 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/48083]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Cui, Dongmei |
| 作者单位 | 1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China 3.RIKEN, Adv Sci Inst, Organometall Chem Lab, Wako, Saitama 3510198, Japan |
| 推荐引用方式 GB/T 7714 | Jian, Zhongbao,Cui, Dongmei,Hou, Zhaomin. Rare-Earth-Metal-Hydrocarbyl Complexes Bearing Linked Cyclopentadienyl or Fluorenyl Ligands: Synthesis, Catalyzed Styrene Polymerization, and Structure-Reactivity Relationship[J]. CHEMISTRY-A EUROPEAN JOURNAL,2012,18(9):2674-2684. |
| APA | Jian, Zhongbao,Cui, Dongmei,&Hou, Zhaomin.(2012).Rare-Earth-Metal-Hydrocarbyl Complexes Bearing Linked Cyclopentadienyl or Fluorenyl Ligands: Synthesis, Catalyzed Styrene Polymerization, and Structure-Reactivity Relationship.CHEMISTRY-A EUROPEAN JOURNAL,18(9),2674-2684. |
| MLA | Jian, Zhongbao,et al."Rare-Earth-Metal-Hydrocarbyl Complexes Bearing Linked Cyclopentadienyl or Fluorenyl Ligands: Synthesis, Catalyzed Styrene Polymerization, and Structure-Reactivity Relationship".CHEMISTRY-A EUROPEAN JOURNAL 18.9(2012):2674-2684. |
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来源：化学研究所
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