Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide Amides supported by methylene-linked bis(phenolate) ligands
文献类型：期刊论文
| 作者 | Xu, Xiaoping; Zhang, Zhongjian; Yao, Yingming; Zhang, Yong; Shen, Qi |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2007-10-29 |
| 卷号 | 46期号:22页码:9379-9388 |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/ic701148z |
| 英文摘要 | A series of neutral and anionic bis(phenolate) lanthanide amides were synthesized by general metathesis reactions, and their reactivity was explored. Protolytic ligand exchange reactions of MBMPH2 (MBMP = 2,2'-methyiene bis(6-teq-butyl-4-methyl-phenolate)) with [Ln{N(TMS)(2)}(2)(mu-CI)(THF)](2) JMS = SiMe3) afforded the desired bridged bis(phenolate) lanthanide chlorides [(MBMP)Ln(mu-CI)(THF)(2)](2) [Ln = Nd (1), Yb (2)] in high isolated yields. These lanthanide chlorides were found to be useful precursors for the synthesis of the corresponding lanthanide derivatives. Reactions of 1 and 2 with 2 equiv of NaN(TMS)2 in THF produced the expected neutral bis(phenolate) lanthanide amido complexes (MBMP)Ln[N(TMS)21(THF)2 [Ln = Nd (3), Yb (4)] in high yields. Whereas the reactions of 1 and 2 with LiN(TMS)(2) in a 1:4 molar ratio gave the anionic bis(phenolate) lanthanide amides as discrete ion-pair complexes [Li(THF)41[(MBMP)[Ln N(TMS)2121 [Ln = Nd (5), Yb (6)] in high isolated yields. Further study revealed that 5 and 6 can also be conveniently synthesized in high yields by the direct reactions of MBMPH2 with [Ln{N(TMS)(2)}(2)(mu Cl)(THF)](2) in a 2:1 molar ratio, and then with 4 equiv of (BuLi)-Bu-n. The reactivity of the neutral and anionic bis(phenolate) lanthanide amides was comparatively investigated. It was found that the insertion reactions of carbodiimide into the Ln-N bond of neutral lanthanide amido complexes 3 and 4 gave the anticipated bis(phenolate) lanthanide guanidinate complexes [(mu-0-MBMP)Nd{((PrN)-Pr-i)(2)CN(TMS)(2)}](2) (7) and (MBMP)Yb[((PrN)-Pr-i)(2)CN(TMS)(2)] (8), respectively, in high yields, whereas the similar reaction of carbodiimide with anionic amido complex 5 provided the unexpected ligand-redistributed products, and the homoleptic. ion-pair bis(phenolate) neodymium complex [Li(DME)(2)(THF)][(MBMP)(2)Nd(THF)(2)] (9) was finally isolated as one of the products. Furthermore, the anionic bis(phenolate) lanthanide amides showed higher catalytic activity for the polymerization of E-caprolactone than the neutral ones. All of the complexes were characterized with elemental analysis and IR spectra, and the definitive molecular structures of 1-3 and 5-9 were provided by single-crystal X-ray analyses. |
| 语种 | 英语 |
| WOS记录号 | WOS:000250345400048 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/60943]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Yao, Yingming |
| 作者单位 | 1.Suzhou Univ, Dept Chem & Chem Engn, Key Lab Organ Synth Jiangsu, Suzhou 215006, Peoples R China 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China |
| 推荐引用方式 GB/T 7714 | Xu, Xiaoping,Zhang, Zhongjian,Yao, Yingming,et al. Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide Amides supported by methylene-linked bis(phenolate) ligands[J]. INORGANIC CHEMISTRY,2007,46(22):9379-9388. |
| APA | Xu, Xiaoping,Zhang, Zhongjian,Yao, Yingming,Zhang, Yong,&Shen, Qi.(2007).Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide Amides supported by methylene-linked bis(phenolate) ligands.INORGANIC CHEMISTRY,46(22),9379-9388. |
| MLA | Xu, Xiaoping,et al."Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide Amides supported by methylene-linked bis(phenolate) ligands".INORGANIC CHEMISTRY 46.22(2007):9379-9388. |
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来源：化学研究所
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