Dialkyl Rare Earth Complexes Supported by Potentially Tridentate Amidinate Ligands: Synthesis, Structures, and Catalytic Activity in Isoprene Polymerization
文献类型：期刊论文
| 作者 | Rad'kov, Vassily Yu1; Skvortsov, Grigorii G.1; Lyubov, Dmitry M.1; Cherkasov, Anton V.1; Fukin, Georgy K.1; Shavyrin, Andrei S.1; Cui, Dongmei2; Trifonov, Alexander A.1 |
| 刊名 | EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
 |
| 出版日期 | 2012-05-01 |
| 期号 | 13页码:2289-2297 |
| 关键词 | Lanthanides Ligand Design Polymerization |
| ISSN号 | 1434-1948 |
| DOI | 10.1002/ejic.201101440 |
| 英文摘要 | Two new amidines that contain a pendant Lewis base in the side arm, 2-MeOC6H4NC(tBu)NH(2,6-R2C6H3) (R = Me, iPr), were synthesized and successfully employed as tridentate ligands for the preparation of the dialkyl rare earth complexes [2-MeOC6H4NC(tBu)N(2,6-R2C6H3)]Ln(CH2SiMe3)2(L)n {Ln = Y, Lu; R = Me, iPr; L = thf (n = 2), dme (n = 1)}. These ligands provided enhanced stability for the complexes. The X-ray structure determinations revealed that intramolecular coordination of the 2-MeOC6H4 group is realized if a thf molecule is coordinated to the metal center (Ln = Y, Lu), which results in the coordination number of six. The treatment of complex [2-MeOC6H4NC(tBu)N(2,6-Me2C6H3)]Lu(CH2SiMe3)2(thf) with dme afforded a six-coordinate dme adduct in which the methoxy group of the amidinate ligand has drifted out from the metal coordination sphere. The reaction of [2-MeOC6H4NC(tBu)N(2,6-iPr2C6H3)]Y(CH2SiMe3)2(thf) with 2,6-diisopropylaniline in hexane at 70 degrees C, regardless of the ratio of the reagent, afforded the six-coordinate diamido compound [2-MeOC6H4NC(tBu)N(2,6-iPr2C6H3)]Y(NHC6H3-2,6-iPr2)2(thf), for which intramolecular coordination of the oxygen atom of the side chain was detected by an X-ray study. Complex [2-MeOC6H4NC(tBu)N(2,6-iPr2C6H3)]Y(CH2SiMe3)2(thf) was evaluated as a precatalyst for isoprene polymerization. The ternary system [2-MeOC6H4NC(tBu)N(2,6-iPr2C6H3)]Y(CH2SiMe3)2(thf)/[Ph3C][B(C6F5)4]/AliBu3provided isoprene polymerization with moderate activity but without control of the regioselectivity (3,4-regularity was slightly predominant at 52?%). Nevertheless, high 1,4-trans-selectivity was found (96%) for the 1,4-polyisoprenes. The obtained polyisoprene has a Mn of 13.0 x 10(4) and moderate polydispersity (2.12). |
| 语种 | 英语 |
| WOS记录号 | WOS:000303155200013 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/48231]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Trifonov, Alexander A. |
| 作者单位 | 1.Russian Acad Sci, GA Razuvaev Inst Organometall Chem, Nizhnii Novgorod 603950, Russia 2.Chinese Acad Sci, State Key Lab Polymer Phys & Chem, Changchun Inst Appl Chem, Changchun 130022, Peoples R China |
| 推荐引用方式 GB/T 7714 | Rad'kov, Vassily Yu,Skvortsov, Grigorii G.,Lyubov, Dmitry M.,et al. Dialkyl Rare Earth Complexes Supported by Potentially Tridentate Amidinate Ligands: Synthesis, Structures, and Catalytic Activity in Isoprene Polymerization[J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY,2012(13):2289-2297. |
| APA | Rad'kov, Vassily Yu.,Skvortsov, Grigorii G..,Lyubov, Dmitry M..,Cherkasov, Anton V..,Fukin, Georgy K..,...&Trifonov, Alexander A..(2012).Dialkyl Rare Earth Complexes Supported by Potentially Tridentate Amidinate Ligands: Synthesis, Structures, and Catalytic Activity in Isoprene Polymerization.EUROPEAN JOURNAL OF INORGANIC CHEMISTRY(13),2289-2297. |
| MLA | Rad'kov, Vassily Yu,et al."Dialkyl Rare Earth Complexes Supported by Potentially Tridentate Amidinate Ligands: Synthesis, Structures, and Catalytic Activity in Isoprene Polymerization".EUROPEAN JOURNAL OF INORGANIC CHEMISTRY .13(2012):2289-2297. |
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来源：化学研究所
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