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Organo-functionalized mesoporous supports for Jacobsen-type catalyst: Laponite versus MCM-41

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Abstract

In order to exploit the different textural properties of Laponite and MCM-41, specifically in terms of their external versus internal surface areas, in the covalent anchoring of a chiral Mn(III) salen complex, these materials were functionalized with 3-aminopropyltriethoxysilane (APTES), subsequently activated with sodium ethoxide, and finally used to anchor the Jacobsen catalyst derivative C1. All the materials were characterized by nitrogen elemental analysis, XPS, PXRD, nitrogen adsorption at −196 °C, FTIR and for those with the immobilized complex, they were additionally characterized by Mn AAS. The APTES anchored at the edges of the Laponite single crystals and inside the MCM-41 pores. Moreover, under the same preparative conditions, higher amount of APTES was anchored onto MCM-41 than onto Laponite, which is due to the higher surface area of MCM-41 compared to Laponite, as well as to its more exposed SiO4 tetrahedra. Activation of the two organo-functionalized materials with sodium ethoxide originated anionic nitrogen groups as deduced by the increase of surface sodium content of these materials and N1s binding energy changes, but led to a small decrease in N bulk content as a result of some APTES leaching. Moreover, for MCM-41 some disruption of the silica framework occurred as a consequence of the basic treatment, as suggested by XPS, PXRD, and nitrogen adsorption study. The APTES functionalized Laponite and MCM-41 materials, as well as the activated analogs, were able to anchor C1 through axial coordination of the metal centre to the grafted surface nitrogen atoms. APTES functionalized MCM-41 presented similar complex content to Laponite analog, what points out for the fact that, at least for the bulky complex used in this work, there was no clear benefit in using a material of high internal area; for the ethoxide activated analogs, Laponite showed the highest complex content of all materials, but MCM-41 was able to anchor the lowest complex quantity, probably as a consequence of damaging effect caused by the basic treatment within its porous structure.

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References

  1. Jacobsen EN, Wu MH (1999) In: Pfaltz A, Jacobsen EN, Yamamoto H (eds) Comprehensive asymmetric catalysis. Springer-Verlag, Berlin

    Chapter  Google Scholar 

  2. Katsuki T (1995) Coord Chem Rev 140:189

    Article  CAS  Google Scholar 

  3. McGarrigle EM, Gilheany DG (2005) Chem Rev 105:1563

    Article  CAS  Google Scholar 

  4. Choudary BM, Chowdari NS, Kantam ML, Santhi PL (2001) Catal Lett 76:213

    Article  CAS  Google Scholar 

  5. Park DW, Choi SD, Choi SJ, Lee CY, Kim GJ (2002) Catal Lett 78:145

    Article  CAS  Google Scholar 

  6. Piaggio P, Langham C, McMorn P, Bethell D, Bulman-Page PC, Hancock FE, Sly C, Hutchings GJ (2000) J Chem Soc Perkin Trans 2:143

    Article  Google Scholar 

  7. Bigi F, Moroni L, Maggi R, Satori G (2002) Chem Commun 716:716

    Article  Google Scholar 

  8. Kim GJ, Kim SH (1999) Catal Lett 57:139

    Article  CAS  Google Scholar 

  9. Zhang HS, **ang J, **ao LC (2005) J Mol Catal A Chem 238:175

    Article  CAS  Google Scholar 

  10. Kureshy RI, Ahmad I, Khan NH, Abdi SHR, Singh S, Pandia PH, Jasra RV (2005) J Catal 235:28

    Article  CAS  Google Scholar 

  11. **ang S, Zhang Y, **n Q, Li C (2002) Chem Commun 2696

  12. **a Q-H, Ge H-Q, Ye C-P, Liu Z-M, Su K-X (2005) Chem Rev 105:1603

    Article  CAS  Google Scholar 

  13. Zhang H, **ang S, Li C (2005) Chem Commun 1209

  14. Kim G-J, Shin J-H (1999) Tetrahedron Lett 40:6827

    Article  CAS  Google Scholar 

  15. Sabater MJ, Corma A, Domenech A, Fornes V, Garcia H (1997) Chem Commun 1285

  16. Heinrichs C, Holderich WF (1999) Catal Lett 58:75

    Article  CAS  Google Scholar 

  17. Gbery G, Zsigmond A, Balkus KJ Jr (2001) Catal Lett 74:77

    Article  CAS  Google Scholar 

  18. Reger TS, **da KD (2000) J Am Chem Soc 122:6929

    Article  CAS  Google Scholar 

  19. Angelino MD, Laibinis PEJ (1999) Polym Sci A Polym Chem 37:3888

    Article  CAS  Google Scholar 

  20. Song CE, Roh EJ, Yu BM, Chi DY, Kim SC, Lee KJ (2000) Chem Commun 615

  21. Minutolo F, Pini D, Petri A, Salvadori P (1996) Tetrahedron Asym 7:2293

    Article  CAS  Google Scholar 

  22. Canali L, Cowan E, Deleuze H, Gibson CL, Sherrington DC (2000) J Chem Soc Perkin Trans 2055

  23. Kureshy RI, Khan NH, Abdi SHR, Ahmad I, Singh S, Jasra RV (2003) Catal Lett 91:207

    Article  CAS  Google Scholar 

  24. Fraile JM, García JI, Massam JA, Mayoral JA (1998) J Mol Catal A Chem 136:47

    Article  CAS  Google Scholar 

  25. Kureshy RI, Khan NH, Abdi SHR, Ahmad I, Singh S, Jasra RV (2004) J Catal 221:234

    Article  CAS  Google Scholar 

  26. Silva AR, Vital J, Figueiredo JL, Freire C, Castro B (2003) New J Chem 27:1511

    Article  CAS  Google Scholar 

  27. Silva AR, Castro B, Freire C (2004) Carbon 42:3027

    Article  CAS  Google Scholar 

  28. Silva AR, Budarin V, Clark JH, Castro B, Freire C (2005) Carbon 43:2096

    Article  CAS  Google Scholar 

  29. Baleizão C, Gigante B, Sabater MJ, Garcia H, Corma A (2002) Appl Catal A Gen 228:279

    Article  Google Scholar 

  30. Shylesh S, Mirajkar SP, Singh AP (2005) J Mol Catal A Chem 239:57

    Article  CAS  Google Scholar 

  31. Zhou XG, Yu XQ, Huang JS, Li SG, Li LS, Che CM (1999) Chem Commun 1789

  32. Dioos BML, Geurts WA, Jacobs PA (2004) Catal Lett 97:125

    Article  CAS  Google Scholar 

  33. Serrano DP, Aguado J, Garcia RA, Vargas C (2005) Stud Surf Sci Catal B 158:1493

    Article  Google Scholar 

  34. Wheeler PA, Wang J, Baker J, Mathias LJ (2005) Chem Mater 17:3012

    Article  CAS  Google Scholar 

  35. Herrera NN, Letoffe J-M, Reymond J-P, Bourgeat-Lami E (2005) J Mater Chem 15:863

    Article  CAS  Google Scholar 

  36. Herrera NN, Letoffe J-M, Putaux JL, David L, Bourgeat-Lami E (2004) Langmuir 20:1564

    Article  CAS  Google Scholar 

  37. Park M, Shim IK, Jung EY (2004) Phys Chem Solids 65:499

    Article  CAS  Google Scholar 

  38. Biernacka IK, Silva AR, Carvalho AP, Pires J, Freire C (2005) Langmuir 21:10825

    Article  Google Scholar 

  39. Pereira C, Patrício S, Silva AR, Magalhães AL, Carvalho AP, Pires J, Freire C (2007) J Colloid Interface Sci 316:570

    Article  CAS  Google Scholar 

  40. Pereira C, Silva AR, Carvalho AP, Pires J, Freire C (2008) J Mol Catal A Chem 283:5

    Article  CAS  Google Scholar 

  41. Jia M, Seifert A, Thiel WR (2003) Chem Mater 15:2174

    Article  CAS  Google Scholar 

  42. Baleizão C, Gigante B, Garcia H, Corma A (2003) J Catal 5:99

    Google Scholar 

  43. Das P, Silva AR, Carvalho AP, Pires J, Freire C (2008) Colloids Surf A: Physicochem Eng Aspects 329:190

    Article  CAS  Google Scholar 

  44. Das P, Silva AR, Carvalho AP, Pires J, Freire C (2009) Catal Lett (in press). doi:https://doi.org/10.1007/s10562-008-9793-x

    Article  Google Scholar 

  45. Grün M, Unger KK, Matsumoto A, Tsutsumi K (1997) In: McEnaney B, Mays TJ, Rouquerol J, Rodríguez-Reinoso F, Sing K, Unger KK (eds) Characterisation of porous solids IV. The Royal Society of Chemistry, London

    Google Scholar 

  46. Schmidt R, Stöcker M, Hansen E, Akporiaye D, Ellestad OH (1995) Microporous Mater 3:443

    Article  CAS  Google Scholar 

  47. Rouquerol F, Rouquerol J, Sing K (1999) Adsorption by powders & porous solid. Academic Press, London

    Google Scholar 

  48. Benazilla M, Manne S, Laney DE, Lyubchenko YL, Hansma HG (1995) Langmuir 10:665

    Google Scholar 

  49. Tatsumi T (2005) Proceedings of 15th Saudi-Japan joint symposium, Dahram, Saudi Arabia

  50. Handbook of chemistry and physics, 53rd edn. CRC Press, Boca Raton, 1972

  51. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Pure Appl Chem 57:603

    Article  CAS  Google Scholar 

  52. Barret EP, Joyner LG, Halenda PP (1951) J Am Chem Soc 73:373

    Article  Google Scholar 

  53. Lukens WJ Jr, Schmidt-Winkel P, Zhao D, Feng J, Stucky GD (1999) Langmuir 15:5403

    Article  CAS  Google Scholar 

  54. Zhao XS, Lu GQ (1998) J Phys Chem B 102:1556

    Article  CAS  Google Scholar 

  55. Gavrilko T, Gnatyuk I, Puchkovskaya G, Goltsov Y, Matkovskaya L, Baran J, Ratajczak H (2000) Vib Spectrosc 23:199

    Article  CAS  Google Scholar 

  56. Borodko Y, Ager JWIII, Marti GE, Hong H, Niesz K, Somorjai GA (2005) J Phys Chem B 109:17386

    Article  CAS  Google Scholar 

  57. Prado AGS, Airoldi C (2002) J Mater Chem 12:3823

    Article  CAS  Google Scholar 

  58. Bourlinos AB, Simopoulos A, Boukos N, Petridis D (2001) J Phys Chem B 105:7432

    Article  CAS  Google Scholar 

  59. Igarashi N, Koyano KA, Tanaka Y, Nakata S, Hashimoto K, Tatsumi T (2003) Microporous Mesoporous Mater 59:43

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was funded by Fundação para a Ciência e a Tecnologia (FCT) and FEDER, through the project ref. POCI/CTM/56192/2004. PD thanks FCT for a Post-Doctoral fellowship.

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Author notes

  1. Pankaj Das

    Present address: Department of Chemistry, Dibrugarh University, Dibrugarh, Assam, 786 004, India

  2. Ana Rosa Silva

    Present address: Unilever R&D, Port Sunlight, Bebington, UK

Authors and Affiliations

  1. REQUIMTE, Departamento de Química, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 4169-007, Porto, Portugal

    Pankaj Das, Ana Rosa Silva & Cristina Freire

  2. Departamento de Química e Bioquímica and CQB, Faculdade de Ciências, Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016, Lisbon, Portugal

    Ana P. Carvalho & João Pires

Authors
  1. Pankaj Das
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  2. Ana Rosa Silva
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  3. Ana P. Carvalho
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  5. Cristina Freire
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Correspondence to João Pires or Cristina Freire.

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Das, P., Silva, A.R., Carvalho, A.P. et al. Organo-functionalized mesoporous supports for Jacobsen-type catalyst: Laponite versus MCM-41. J Mater Sci 44, 2865–2875 (2009). https://doi.org/10.1007/s10853-009-3379-x

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