Skip to main content
SpringerLink
Log in

Preparation of MCM-41-supported chiral Salen Mn (III) catalysts and their catalytic properties in the asymmetric epoxidation of olefins

  • Articles
  • Organic Chemistry
  • Published:
Chinese Science Bulletin

Abstract

A secondary amino-modified mesoporous molecular sieve MCM-41 was obtained by reaction of bis(3-(triethoxysilyl)propyl)amine with MCM-41. The chiral Salen-Mn (III) complex was anchored onto the modified MCM-41 by a multi-step grafting method and two heterogenized catalysts with different Mn contents were obtained. The catalysts were characterized by XRD, N2 adsorption, ICP, FT-IR and DR UV-Vis. Their catalysis on asymmetric epoxidation of several olefins was studied with NaClO and m-CPBA as oxidants respectively. It was found that both the activity and enantioselectivity of the catalysts decreased after the homogeneous catalyst was heterogenized. The reasons resulting in the decrease of catalytic performance were discussed.

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. Katsuki T. Chiral metallosalen complexe: structures and catalyst tuning for asymmetric epoxidation and cyclopropopanation. Adv Synth Catal, 2002, 344(2): 131–147

    Article  Google Scholar 

  2. McGarrigle E M, Gilheany D G. Chromium-and manganese-salen promoted epoxidation of alkenes. Chem Rev, 2005, 105(5): 1563–1602

    Article  Google Scholar 

  3. Jacobsen E N, Zhang W, Muci A R, et al. Highly enantioselective epoxidation catalysts derived from 1,2-diaminnocyclohexane. J Am Chem Soc, 1991, 113: 7063–7064

    Article  Google Scholar 

  4. Bryliakov K P, Kholdeeva O A, Vanina M P, et al. Role of MnIV species in Mn (salen) catalyzed enantioselective aerobic epoxidation of alkenes: an EPR study. J Mol Catal A: Chem, 2002, 178: 47–53

    Article  Google Scholar 

  5. Canali L, Sherrington D C, Deleuze H. Synthesis of resins with pendently-bound chiral manganese-salen complexes and used as heterogeneous asymmetric alkene epoxidation catalysts. React Funct Polym, 1999, 40: 155–168

    Article  Google Scholar 

  6. Song C E, Roh E J, Yu B M, et al. Heterogeneous asymmetric epoxidation of alkenes catalysed by a polymer-bound (pyrrolidine salen) manganese (III) complex. Chem Commun, 2000, (7): 615–616

  7. Sabater M J, Corma A, Domenech A, et al. Chiral salen manganese complex encapsulated within zeolite Y: a heterogeneous enantiose-lective catalyst for the epoxidation of alkenes. Chem Commun, 1997, (14): 1285–1286

  8. Xiang S, Zhang Y L, Xin Qin, et al. Enantioselective epoxidation of olefins catalyzed by Mn (salen)/MCM-41 synthesized with a new anchoring method. Chem Commum, 2002, 2696–2697

  9. Zhang H D, Li C. Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn (salen) catalyst immobilized in mesoporous materials. Tetrahedron, 2006, 62: 6640–6649

    Article  Google Scholar 

  10. Beck J S, Vartuli J C, Roth W J, et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates. J Am Chem Soc, 1992, 114(27): 10834–10842

    Article  Google Scholar 

  11. Kresge C T, Leonowicz M E, Roth W J, et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature, 1992, 359(6397): 71–711

    Article  Google Scholar 

  12. Long Y C, Dong W Y, Xu T M, et al. The adsorption isotherms, IR and 29Si MAS NMR spectra of modified MCM-41 molecular sieves. Chin Sci Bull, 1997, 42(9): 938–940

    Google Scholar 

  13. Grǖn M, Unger K K, Matsumoto A, et al. Novel pathways for the preparation of mesoporous MCM-41 material: control of porosity and morphology. Micropor Mesopor Mater, 1999, 27: 207–216

    Article  Google Scholar 

  14. Zhang Y R, Zhao J Q, He L Q, et al. Synthesis and characterization of complexes of Mn(III), Fe(III), Ni(II) and Cu(II) with a new schiff base ligand. Chinese J Inorg Chem (in Chinese), 2005, 21(12): 1871–1874

    Google Scholar 

  15. Park M, Komarneni S. Stepwise functionalization of mesoporous crystalline silica materials. Micropor Mesppor Mater, 1998, 25: 75–80

    Article  Google Scholar 

  16. Kureshy R I, Ahmad I, Khan N H, et al. New immobilized chiral Mn (III) salen complexes on pyridine N-oxide-modified MCM-41 as effective catalysts for epoxidation of nonfunctionalized alkenes. J Catal, 2005, 235: 28–34

    Article  Google Scholar 

  17. Zsigmond Á, Horváth A, Notheisz F. Effect of substituents on the Mn (III) salen catalyzed oxidation of styrene. J Mol Catal A: Chem, 2001, 171(1): 95–102

    Article  Google Scholar 

  18. Varkey S P, Ratnasamy C, Ratnasamy P. Zeolite-encapsulated manganese (III) complex into mesoporous silicates. J Mol Catal A: Chem, 1998, 135(3): 295–306

    Article  Google Scholar 

  19. Palucki M, McCormick G J, Jacobsen E N. Low temperature asymmetric epoxidation of unfunctionalized olefins catalyzed by (Salen) Mn (III) complexes. Tetrahedron Lett, 1995, 36(31): 5454–5460

    Google Scholar 

  20. Srinivasan K, Michaud P, Kochi J K. Epoxidation of olefins with cationic (Salen) MnIII complexes. The modulation of catalytic activity by substituents. J Am Chem Soc, 1986, 108(8): 2309–2320

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Chemical Engineering, Hebei University of Technology, Tianjin, 300130, China

    Zhao DongMin, Zhao JiQuan, Zhao ShanShan, He LeQin & Wang WeiYu

Authors
  1. Zhao DongMin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhao JiQuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhao ShanShan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. He LeQin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wang WeiYu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zhao JiQuan.

Additional information

Supported by the National Natural Science Foundation of China (Grant No. 20376017)

About this article

Cite this article

Zhao, D., Zhao, J., Zhao, S. et al. Preparation of MCM-41-supported chiral Salen Mn (III) catalysts and their catalytic properties in the asymmetric epoxidation of olefins. CHINESE SCI BULL 52, 2337–2344 (2007). https://doi.org/10.1007/s11434-007-0333-7

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-007-0333-7

Keywords

Search

Navigation