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Lanthanide amido complexes incorporating amino-coordinate-lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines.
Inorg Chem. 2012 Jul 02; 51(13):7134-43.IC

Abstract

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 [(Me(3)Si)(2)N](3)Ln(III)(μ-Cl)Li(THF)(3) with 2 equiv of 3-(CyNHCH(2))C(8)H(5)NH in toluene produced the amino-coordinate-lithium bridged bis(indolyl) lanthanide amides [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] (Cy = cyclohexyl, Ind = Indolyl, Ln = Sm (1), Eu (2), Dy (3), Yb (4)) in good yields. Treatment of [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] with THF gave new lanthanide amido complexes [μ-{[η(1):η(1)-3-(CyNHCH(2))Ind](2)Li(THF)}Ln[N(SiMe(3))(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 1-7 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-P bond formation with employment of low catalyst loadings (0.1 mol % for aldehydes and 1 mol % for aldimines) under mild conditions. Thus, it provides a convenient way to prepare both α-hydroxy and α-amino phosphonates.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Zhu X
Laboratory of Functionalized Molecular Solids, Ministry of Education, Institute of Organic Chemistry, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, People's Republic of China.
Wang S
No affiliation info available
Zhou S
No affiliation info available
Wei Y
No affiliation info available
Zhang L
No affiliation info available
Wang F
No affiliation info available
Feng Z
No affiliation info available
Guo L
No affiliation info available
Mu X
No affiliation info available

MeSH

AldehydesAmidesCatalysisCrystallography, X-RayIminesIndolesLanthanoid Series ElementsLigandsLithiumModels, MolecularMolecular StructureOrganometallic CompoundsOrganophosphonates

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

22712783

Citation

Zhu, Xiancui, et al. "Lanthanide Amido Complexes Incorporating Amino-coordinate-lithium Bridged Bis(indolyl) Ligands: Synthesis, Characterization, and Catalysis for Hydrophosphonylation of Aldehydes and Aldimines." Inorganic Chemistry, vol. 51, no. 13, 2012, pp. 7134-43.
Zhu X, Wang S, Zhou S, et al. Lanthanide amido complexes incorporating amino-coordinate-lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines. Inorg Chem. 2012;51(13):7134-43.
Zhu, X., Wang, S., Zhou, S., Wei, Y., Zhang, L., Wang, F., Feng, Z., Guo, L., & Mu, X. (2012). Lanthanide amido complexes incorporating amino-coordinate-lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines. Inorganic Chemistry, 51(13), 7134-43. https://doi.org/10.1021/ic300137r
Zhu X, et al. Lanthanide Amido Complexes Incorporating Amino-coordinate-lithium Bridged Bis(indolyl) Ligands: Synthesis, Characterization, and Catalysis for Hydrophosphonylation of Aldehydes and Aldimines. Inorg Chem. 2012 Jul 2;51(13):7134-43. PubMed PMID: 22712783.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Lanthanide amido complexes incorporating amino-coordinate-lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines. AU - Zhu,Xiancui, AU - Wang,Shaowu, AU - Zhou,Shuangliu, AU - Wei,Yun, AU - Zhang,Lijun, AU - Wang,Fenhua, AU - Feng,Zhijun, AU - Guo,Liping, AU - Mu,Xiaolong, Y1 - 2012/06/19/ PY - 2012/6/21/entrez PY - 2012/6/21/pubmed PY - 2012/10/31/medline SP - 7134 EP - 43 JF - Inorganic chemistry JO - Inorg Chem VL - 51 IS - 13 N2 - 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 [(Me(3)Si)(2)N](3)Ln(III)(μ-Cl)Li(THF)(3) with 2 equiv of 3-(CyNHCH(2))C(8)H(5)NH in toluene produced the amino-coordinate-lithium bridged bis(indolyl) lanthanide amides [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] (Cy = cyclohexyl, Ind = Indolyl, Ln = Sm (1), Eu (2), Dy (3), Yb (4)) in good yields. Treatment of [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] with THF gave new lanthanide amido complexes [μ-{[η(1):η(1)-3-(CyNHCH(2))Ind](2)Li(THF)}Ln[N(SiMe(3))(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 1-7 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-P bond formation with employment of low catalyst loadings (0.1 mol % for aldehydes and 1 mol % for aldimines) under mild conditions. Thus, it provides a convenient way to prepare both α-hydroxy and α-amino phosphonates. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/22712783/Lanthanide_amido_complexes_incorporating_amino_coordinate_lithium_bridged_bis_indolyl__ligands:_synthesis_characterization_and_catalysis_for_hydrophosphonylation_of_aldehydes_and_aldimines_ DB - PRIME DP - Unbound Medicine ER -