Lanthanide Amido Complexes Incorporating Amino-Coordinate-Lithium Bridged Bis(indolyl) Ligands: Synthesis, Characterization, and Catalysis for Hydrophosphonylation of Aldehydes and Aldimines

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• 作者：Xiancui Zhu ; Shaowu Wang ; Shuangliu Zhou ; Yun Wei ; Lijun Zhang ; Fenhua Wang ; Zhijun Feng ; Liping Guo ; Xiaolong Mu
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：July 2, 2012
• 年：2012
• 卷：51
• 期：13
• 页码：7134-7143
• 全文大小：411K
• 年卷期：v.51,no.13(July 2, 2012)
• ISSN：1520-510X

文摘

Two series of new lanthanide amido complexes supported by bis(indolyl) ligands with amino-coordinate-lithium as a bridge were synthesized and characterized. The interactions of [(Me₃Si)₂N]₃Ln^III(渭-Cl)Li(THF)₃ with 2 equiv of 3-(CyNHCH₂)C₈H₅NH in toluene produced the amino-coordinate-lithium bridged bis(indolyl) lanthanide amides [渭-{[畏¹:畏¹:畏¹:畏¹-3-(CyNHCH₂)Ind]₂Li}Ln[N(SiMe₃)₂]₂] (Cy = cyclohexyl, Ind = Indolyl, Ln = Sm (1), Eu (2), Dy (3), Yb (4)) in good yields. Treatment of [渭-{[畏¹:畏¹:畏¹:畏¹-3-(CyNHCH₂)Ind]₂Li}Ln[N(SiMe₃)₂]₂] with THF gave new lanthanide amido complexes [渭-{[畏¹:畏¹-3-(CyNHCH₂)Ind]₂Li(THF)}Ln[N(SiMe₃)₂]₂] (Ln = Eu (5), Dy (6), Yb (7)), which can be transferred to amido complexes 2, 3, and 4 by reflux the corresponding complexes in toluene. Thus, two series of rare-earth-metal amides could be reciprocally transformed easily by merely changing the solvent in the reactions. All new complexes 1鈥?b>7 are fully characterized including X-ray structural determination. The catalytic activities of these new lanthanide amido complexes for hydrophosphonylation of both aromatic and aliphatic aldehydes and various substituted aldimines were explored. The results indicated that these complexes displayed a high catalytic activity for the C鈥揚 bond formation with employment of low catalyst loadings (0.1 mol鈥? for aldehydes and 1 mol鈥? for aldimines) under mild conditions. Thus, it provides a convenient way to prepare both 伪-hydroxy and 伪-amino phosphonates.