Immobilization of Jacobsen type catalysts on modified silica


  • Jairo Cubillos Pedagogical and Technological University of Colombia
  • Edwing Grajales University of Antioquia
  • Santiago Vásquez University of Antioquia
  • Consuelo Montes de Correa University of Antioquia



Jacobsen type catalysts, Mn(III) salen complexes, immobilization, modified SiO2, amino-functionalization, epoxidation, R-( )-limonene


Several immobilized Jacobsen type catalysts were covalently anchored on modified SiO2 using 3-aminopropyltriethoxysilane (3-APTES) as a reactive surface modifier. Characterization of the heterogeneous catalysts, as well as their precursors, by FTIR, DR UV-VIS, TGA and AAS confirms the successful immobilization of chiral Mn(III) salen complexes. These catalysts were examined for the diastereoselective epoxidation of R-(+)-limonene with in situ generated dimethyldioxirane (DMD) as oxidizing agent, yielding 1,2-epoxide as the main product. When compared to homogeneous catalysts, under similar experimental conditions, only a slight selectivity decrease over heterogeneous catalysts was observed. The immobilized catalysts were used three times maintaining the initial selectivity. However, after reusing them more than three times, selectivity to 1,2-epoxide decreased. FTIR results suggest partial degradation of the catalytic species. Despite the immobilization method was chosen to minimize changes in the structure of the homogeneous catalysts the diastereoselectivity (d.e.) of heterogeneous catalysts underwent a remarkable decay.

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Author Biographies

Jairo Cubillos, Pedagogical and Technological University of Colombia

School of Chemical Sciences, Faculty of Sciences.

Edwing Grajales, University of Antioquia

Environmental Catalysis Group, Faculty of Engineering.

Santiago Vásquez, University of Antioquia

Environmental Catalysis Group, Faculty of Engineering.

Consuelo Montes de Correa, University of Antioquia

Environmental Catalysis Group, Faculty of Engineering.


C. T. Dalton, K. M. Ryan, V. M. Wall, C. Bousquet, D. G. Gilheany. “Recent progress towards the understanding of metal–salen catalysed asymmetric alkene epoxidation”. Top. Catal. Vol. 5. 1998. pp. 75-91.

Q. H. Xia, H. Q. Ge, C. P. Ye, Z. M. Liu, K. X. Su. “Advances in homogeneous and heterogeneous catalytic asymmetric epoxidation”. Chem. Rev. Vol. 105. 2005. pp. 1603-1662.

P. Mastrorilli, C. F. Nobile. “Supported catalysts from polymerizable transition metal complexes”. Coord. Chem. Vol. 248. 2004. pp. 377-395.

M. Silva, C. Freire, B. de Castro, J. L. Figueiredo. “Styrene oxidation by manganese Schiff base complexes in zeolite structures”. J. Mol. Catal. A: Gen. Vol. 258. 2006. pp. 327-333.

J. M. Thomas, R. Raja. “Catalytic significance of organometallic compounds immobilized on

mesoporous silica: economically and environmentally important examples”. J. Organomet. Chem. Vol. 689. 2004. pp. 4110-4124.

P. Oliveira, A. Machado, A. M. Ramos, I. Fonseca, F. M. Braz Fernandes, A. M. Botelho do Rego, J. Vital. “MCM-41 anchored manganese salen complexes as catalysts for limonene oxidation”. Microporous Mesoporous Mater. Vol. 120. 2009. pp. 432-440.

C. Baleizaõ, H. García. “Chiral salen complexes: anoverview to recoverable and reusable homogeneous and heterogeneous catalysts”. Chem. Rev. Vol. 106. 2006. pp. 3987-4043.

J. A. Cubillos, W. F. Hölderich. “Jacobsen’s catalyst anchored on Al-MCM-41 and NH2 group modified Si-MCM-41 as heterogeneous enantioselective epoxidation catalyst using in situ generated dimethyldioxirane as oxidant”. Rev. Fac.Ing. Univ. Antioquia. Vol. 41. 2007. pp. 31-47.

J. Reyes, J. A. Cubillos, A. L. Villa, C. Montes de Correa. “Efecto de la quiralidad del sustrato y del catalizador en la epoxidación diastereoselectiva de R-(+)-limoneno con complejos de salen de manganeso(III)” Rev. Fac. Ing. Univ. Antioquia. Vol. 48. 2009. pp. 18-26.

J. A. Cubillos, I. D. Montilla, C. Montes de Correa. “Separación del catalizador de Jacobsen en la epoxidación enantioselectiva de cis-cinamato de etilo bajo condiciones homogéneas” Rev. Fac. Ing. Univ. Antioquia. Vol. 47. 2009. pp. 9-19.

J. A. Cubillos, I. D. Montilla, C. Montes de Correa. “Easy separation and reutilization of the Jacobsen catalyst in olefin oxidation”. Appl. Catal., A. Vol. 366. 2009. pp. 348-352.

J. A. Cubillos, S. Vásquez, C. Montes de Correa. “Salen manganese (III) complexes as catalyst for R-(+)-limonene oxidation”. Appl. Catal. A. Vol. 373. 2010. pp. 57-65.

M. A. Uguina, J. A. Delgado, A. Rodríguez, J. Carretero, D. Gómez-Díaz. “Alumina as heterogeneous catalyst for the regioselective epoxidation of terpenic diolefins with hydrogen peroxide”. J. Mol. Catal. A: Chem. Vol. 256. 2006. pp. 208-215.

L. Deng, E. N. Jacobsen. “A practical, highly enantioselective synthesis of the Taxol side chain via asymmetric catalysis”. J. Org. Chem. Vol. 57. 1992. pp. 4320-4323.

R. I. Kureshy, I. Ahmad, N-u. H. Khan, S. H. R. Abdi, K. Pathak, R. V. Jasra. “ Encapsulation of a chiral MnIII(salen) complex in ordered mesoporous silicas: an approach towards heterogenizing asymmetric epoxidation catalysts for non-functionalized alkenes”. Tetrahedron: Asymmetry Vol. 16. 2005. pp. 3562- 3569.

K. Yu, Z. Gu, R. Ji, L-L. Lou, F. Ding, C. Zhang, S. Liu. “Effect of pore size on the performance of mesoporous material supported chiral Mn(III) salen complex for the epoxidation of unfunctionalized olefins”. J. Catal. Vol. 252. 2007. pp. 312-320.

K. Yu, L.-L. Lou, C. Lai, S. Wang, F. Ding, S. Liu. “Asymmetric epoxidation of unfunctionalized olefins catalyzed by Mn(III) salen complex immobilized on MCM-48”. Catal. Commun. Vol. 7. 2006. pp. 1057- 1060.

J. Reyes. Epoxidación diastereoselectiva de R-(+)- limoneno y α-(–)-pineno con complejos de salen de manganeso inmovilizados en MCM-41. Maestría en Ingeniería. Universidad de Antioquia, 2008. pp. 74-79.

R. Bai, X. FU, H. Bao. W. Ren. “Chiral Salen Mn(III) complex axial coordination immobilized on diamine modified ZSPP and their catalytic epoxidation of styrene”. Catal. Commun. Vol. 9. 2008. pp. 1588- 1594.

T. Luts, W. Suprun, D. Hofmann, O. Klepel, H. Papp. “Epoxidation of olefins catalyzed by novel Mn(III) and Mo(IV) salen complexes immobilized on mesoporous silica gel: Part I. Synthesis and characterization of homogeneous and immobilized Mn(III) and Mo(IV) Salen complexes”. J. Mol. Catal. A: Chem. Vol.261. 2007. pp. 16-23.

L-L. Lou, K. Yu, F. Ding, X. Peng, M. Dong, C. Zhang, S. Liu. “Covalently anchored chiral Mn(III) salencontaining ionic species on mesoporous materials as effective catalysts for asymmetric epoxidation of unfunctionalized olefins”. J. Catal. Vol.249. 2007. pp. 102-110.

J. A. Cubillos, M. Vargas, J. Reyes, A. Villa, C. Montes de Correa. “Effect of the substrate and catalyst chirality on the diastereoselective epoxidation of limonene using Jacobsen-type catalysts”. Chirality. Vol.22. 2010. pp. 403-410.

L. Saikia, D. Srinivas, P. Ratnasamy. “Chemo-, regioand stereo-selective aerial oxidation of limonene to the endo-1,2-epoxide over Mn(Salen)-sulfonated SBA- 15”. Appl. Catal., A. Vol. 309. 2006. pp. 144-154.



How to Cite

Cubillos, J., Grajales, E., Vásquez, S., & Montes de Correa, C. (2013). Immobilization of Jacobsen type catalysts on modified silica. Revista Facultad De Ingeniería Universidad De Antioquia, (57), 38–48.

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