Skip to main content
SpringerLink
Log in

Synthesis and characterization of N-aryloxo-functionalized β-ketoiminate rare-earth complexes and their catalytic activity for the polymerization of ɛ-caprolactone

  • Articles / Inorganic Chemistry
  • Published:
Chinese Science Bulletin

Abstract

The synthesis and characterization of dimeric rare-earth amides stabilized by a dianionic N-aryloxo functionalized β-ketoiminate ligand are described. Reactions of 4-(2-hydroxy-5-methyl-phenyl) imino-2-pentanone (LH2) with Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 in a 1:1 molar ratio in THF gave the dimeric rare-earth amido complexes [LLn{N(SiMe3)2}(THF)]2 [Ln = Nd (1), Sm (2), Yb (3), Y (4)]. These complexes were well characterized, and the definitive molecular structures of complexes 3 and 4 were determined. It was found that complexes 1–4 can initiate the ring-opening polymerization of ɛ-caprolactone, and the ionic radii of the central metals have significant effect on the catalytic activity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Tang L M, Li Y G, Ye W P, et al. Ethylene-propylene copolymerization with bis(β-enaminoketonato) titanium complexes activated with modified methylaluminoxane. J Polym Sci Part A: Polym Chem, 2006, 44: 5846–5854

    Article  Google Scholar 

  2. Zhang D, Jin G. X, Weng L H, et al. Synthesis, molecular structures, and norbornene addition polymerization activity of the neutral nickel catalysts supported by β-diketiminato [N,N], ketiminato [N,O], and Schiff-base [N,O] ligands. Organometallics, 2004, 23: 3270–3275

    Article  Google Scholar 

  3. He X H, Yao Y Z, Luo X, et al. Nickel(II) complexes bearing N,O-chelate ligands: Synthesis, solid-structure characterization, and reactivity toward the polymerization of polar monomer. Organometallics, 2003, 22: 4952–4957

    Article  Google Scholar 

  4. Huang Y B, Jin G X. Half-sandwich chromium(III) complexes bearing β-ketoiminato and β-diketiminate ligands as catalysts for ethylene polymerization. Dalton Trans, 2009, 767–769

  5. Huang Y B, Tang G R, Jin G X. Binuclear nickel and copper complexes with bridging 2,5-diamino-1,4-benzoquinonediimines: Synthesis, structures, and catalytic olefin polymerization. Organometallics, 2008, 27: 259–269

    Article  Google Scholar 

  6. Tang H Y, Chen H Y, Huang J H, et al. Synthesis and structural characterization of magnesium ketiminate complexes: Efficient initiators for the ring-opening polymerization of L-lactide. Macromolecules, 2007, 40: 8855–8860

    Article  Google Scholar 

  7. Doherty S, Errington R J, Housley N, et al. Dimeric aluminum chloride complexes of N-alkoxyalkyl-β-ketoimines: Activation with propylene oxide to form efficient lactide polymerization catalysts. Organometallics, 2004, 23: 2382–2388

    Article  Google Scholar 

  8. Jin X, Novak B M. Synthesis of β-iminoaminate zirconium complexes and their application in ethylene polymerization. Macromolecules, 2000, 33: 6205–6207

    Article  Google Scholar 

  9. Jäger E G, Müller K. Structure reactivity relations of coordinatively unsaturated chelate complexes. III. acceptor tendency of nickel and cobalt chelates with tridentate di-anionic Schiff base ligands. Z Anorg Allg Chem, 1981, 482: 201–216

    Article  Google Scholar 

  10. Peng H M, Zhang Z Q, Qi R P, et al. Synthesis, reactivity, and characterization of sodium and rare-earth metal complexes bearing a dianionic N-aryloxo-functionalized β-ketoiminate ligand. Inorg Chem, 2008, 47: 9828–9835

    Article  Google Scholar 

  11. Zhou S L, Wang S W, Yang G S, et al. Synthesis, structure, and catalytic activity of tetracoordinate lanthanide amides [(Me3Si)2N]3 Ln(μ-Cl)Li(THF)3 (Ln= Nd, Sm, Eu). Polyhedron, 2003, 22: 1019–1024

    Article  Google Scholar 

  12. Yao Y M, Mao L S, Lu X H, et al. Synthesis, characterization and crystal structure of neutral homoleptic lanthanide amide Yb(NPh2)3 (THF)2. J Rare Earths, 2002, 20: 592–595

    Google Scholar 

  13. Yao Y M, Xu X P, Liu B, et al. Carbon-bridged bis(phenolato) lanthanide alkoxides: Syntheses, structures, and their application in the controlled polymerization of ɛ-caprolactone. Inorg Chem, 2005, 44: 5133–5140

    Article  Google Scholar 

  14. Deacon G B, Nickle S, Mackinnon P I, et al. Organoamido-and aryloxo-lanthanoids. II. Preparation of tris(2,6-diphenylphenoxo)-lanthanoid (III) complexes and the X-ray structures of low-coordi- nate [Yb(O-2,6-Ph2C6H3)3] containing an intramolecular chelate Yb-π-arene interaction, and [Yb(O-2,6-Ph2C6H3)3(THF)2]. Aust J Chem, 1990, 43: 1245–1257

    Google Scholar 

  15. Yao Y M, Zhang Z Q, Peng H M, et al. Synthesis and structural characterization of β-diketiminate-lanthanide amides and their catalytic activity for the polymerization of methyl methacrylate and ɛ-caprolactone. Inorg Chem, 2006, 45: 2175–2183

    Article  Google Scholar 

  16. Xu X P, Zhang Z J, Yao Y M, et al. Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide amides supported by methylene-linked bis(phenolate) ligands. Inorg Chem, 2007, 46: 9379–9388

    Article  Google Scholar 

  17. Yasuda H, Yamamoto H, Yamashita M, et al. Synthesis of high molecular weight poly(methyl methacrylate) with extremely low polydispersity by the unique function of organolanthanide(III) complexes. Macromolecules, 1993, 26: 7134–7143

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou, 215123, China

    XiangZong Han, LiangLiang Wu, YingMing Yao, Yong Zhang & Qi Shen

Authors
  1. XiangZong Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. LiangLiang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. YingMing Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Qi Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to YingMing Yao.

Additional information

Supported by the National Natural Science Foundation of China (Grant No. 20771078), Natural Science Foundation of Jiangsu Province (Grant No. BK2007505), Major Basic Research Project of Natural Science Foundation of Jiangsu Higher Education Institutions (Grant No. 07KJA15014), and Qing Lan Project

About this article

Cite this article

Han, X., Wu, L., Yao, Y. et al. Synthesis and characterization of N-aryloxo-functionalized β-ketoiminate rare-earth complexes and their catalytic activity for the polymerization of ɛ-caprolactone. Chin. Sci. Bull. 54, 3795–3800 (2009). https://doi.org/10.1007/s11434-009-0514-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-009-0514-7

Keywords

Search

Navigation