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 ZB ; Cui DM ; Hou ZM |
| 刊名 | chemistry-a european journal
 |
| 出版日期 | 2012 |
| 卷号 | 18期号:9页码:2674-2684 |
| ISSN号 | 0947-6539 |
| 关键词 | HALF-SANDWICH COMPLEXES SINGLE-SITE CATALYSTS MONOANIONIC ANCILLARY LIGANDS ALLYL LANTHANIDE COMPLEXES FULL-SIZE RANGE C-H ACTIVATION SYNDIOTACTIC POLYSTYRENE OLEFIN-POLYMERIZATION ALKYL COMPLEXES STEREOSPECIFIC POLYMERIZATION |
| 通讯作者 | cui dm |
| 中文摘要 | 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. |
| 收录类别 | SCI收录期刊论文 |
| 语种 | 英语 |
| WOS记录号 | WOS:000300691000030 |
| 公开日期 | 2013-06-08 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/48339]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_期刊论文 |
| 推荐引用方式 GB/T 7714 | Jian ZB,Cui DM,Hou ZM. 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 ZB,Cui DM,&Hou ZM.(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 ZB,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. |
入库方式： OAI收割
来源：长春应用化学研究所
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