Abstract
An account of biomimetic oxidations by metal phthalocyanines, tri- and tetra-aza macrocycles, Schiff bases (salen and saloph), dimeric Cu-acetate and Co-Mn-acetate complexes encapsulated in zeolite-Y and molecular sieves is reported. The selective oxidation reactions investigated include epoxidation of styrene, hydroxylation of phenol, oxidation of p-xylene to terephthalic acid, ethylbenzene to acetophenone and cyclohexane, cyclohexanol and cyclohexanone to adipic acid. In all these reactions, the encapsulated metal complexes exhibit enhanced activity or selectivity compared to the “neat” complexes. The reasons for the enhanced activity of metal complexes upon encapsulation in zeolites are reported.
Similar content being viewed by others
References
H. A. O. Hill, P. J. Sadler and A. J. Thomson (eds), Metal Sites in Proteins and Models: Iron Centers, Structure & Bonding, Vol. 88 (Springer-Verlag, Berlin, 1997).
R. D. Jones, D. A. Summerville and F. Basolo, Chem.Rev. 79 (139) 1979.
N. Herron, CHEMTECH 19 (1989) 542.
K. J. Balkus Jr. and A. G. Gabrielov, J. Incl. Phenom. Mol. Recog. Chem. 21 (1995) 159.
J. J. E. Moreai and M. W. C. Man, Coord. Chem. Rev. 178–180 (1998) 1073.
D. Brunel, N. Bellocq, P. Sutra, A. Cauvel, M. Lasperas, P. Moreai, F. Di Renzo, A. Galarneai and F. Fajula, Coord. Chem. Rev. 178–180 (1998) 1085.
A. Choplin and F. Quignard, Coord. Chem. Rev. 178–180 (1998) 1679.
D. E. De Vos, M. Dams, B. F. Sels and P. A. Jacobs, Chem. Rev. 102 (2002) 3615.
N. Herron, Inorg. Chem. 25 (1986) 4714.
R. F. Parton, I. Vankelecom, C. P. Bezoukhanova, M. Casselman, J. Uytterhoeven and P. A. Jacobs, Nature 370 (1994) 541.
R. F. Parton, C. P. Bezoukhanova, F. Thibault-Starzyk, R. A. Raynders, P. J. Grobet and P. A. Jacobs, Stud. Surf. Sci. Catal. 84 (1994) 813.
R. F. Parton, C. P. Bezoukhanova, J. Grobet, P. J. Grobet and P. A. Jacobs, Stud. Surf. Sci. Catal. 83 (1994) 371.
K. J. Balkus Jr., M. Eissa and R. Lavado, J. Am. Chem. Soc. 117 (1995) 10753.
E. Armengol, A. Corma, V. Fornes, H. Garcia and J. Primo, Appl. Catal. A: Gen. 181 (1999) 305.
P. P. Knops-Gerrits, D. E. De Vos, F. Thibault-Starzyk and P. A. Jacobs, Nature 369 (1994) 543.
D. E. De Vos, S. De Wildeman, B. F. Sels, P. J. Grobet and P. A. Jacobs, Angew. Chem. Int. Ed. Engl. 38 (1999) 1033.
Y. V. S. Rao, D. E. De Vos, T. Bein and P. A. Jacobs, Chem. Commun. (1997) 355.
P. E. F. Neys, I. F. J. Vankelecom, R. F. Parton, W. Dahaen, G. L'abbe and P. A. Jacobs, J. Mol. Catal. A: Chem. 126 (1997) L9.
B. P. Murphy, Coord. Chem. Rev. 124 (1993) 63.
J. Woltinger, J. E. Backvall and A. Zsigmond, Chem. Eur. J. 5 (1999) 1460.
A. Zsigmond, F. Notheisz, Z. Frater and J. E. Backvall, Stud. Surf. Sci. Catal. 108 (1997) 453.
A. Zsigmond, F. Notheisz, Z. Szegletes and J. E. Backvall, Stud. Surf. Sci. Catal. 94 (1995) 728.
H. Diegrubber, P. J. Plath and G. Schulz-Ekloff, J. Mol. Catal. 24 (1984) 115.
S. B. Ogunwumi and T. Bein, Chem. Commun. (1997) 901.
M. J. Sabater, A. Corma, A. Domenech, V. Fornes and H. Garcia, Chem. Commun. (1997) 1285.
P. Piaggio, P. McMorn, C. Langham, D. Bethell, P. C. Bulman-Page, F. E. Hancock and G. J. Hutchings, New J. Chem. (1998) 1167.
S. Seelan, A. K. Sinha, D. Srinivas and S. Sivasanker, J. Mol. Catal. A: Chem. 157 (2000) 163.
S. Seelan, D. Srinivas, M. S. Agashe, N. E. Jacob and S. Sivasanker, Stud. Surf. Sci. Catal. 135 (2001) 2224.
S. Seelan, A. K. Sinha, D. Srinivas and S. Sivasanker, Bull. Catal. Soc. India 1 (2002) 29.
R. Raja and P. Ratnasamy, Stud. Surf. Sci. Catal. 101 (1996) 181.
V. Ramaswamy, M. Sivarama Krishnan, A. V. Ramaswamy, J. Mol. Catal., A: Chem. 181 (2002) 81.
R. Raja and P. Ratnasamy, Appl. Catal., A: Gen. 158 (1997) L7.
R. Raja, C. R. Jacob and P. Ratnasamy, Catal. Today 49 (1999) 171.
R. Raja and P. Ratnasamy, Catal. Lett. 48 (1997) 1.
R. Raja and P. Ratnasamy, J. Catal. 170 (1997) 244.
D. E. De Vos, B. F. Sels, M. Reynaers, Y. V. Subba Rao and P. A. Jacobs, Tetrahedron Lett. 39 (1998) 3221.
J. R. L. Smith and G. B. Shul'pin, Tetrahedron Lett. 39 (1998) 4909.
G. B. Shul'pin, G. Suss-Fink and L. S. Shul'pin, J. Mol. Catal. A: Chem. 170 (2001) 17.
T. H. Bennur, S. Sabne, S. S. Deshpande, D. Srinivas and S. Sivasanker, J. Mol. Catal. A: Chem. 185 (2002) 71.
T. H. Bennur, D. Srinivas and S. Sivasanker, unpublished results.
S. P. Varkey, C. Ratnasamy and P. Ratnasamy, J. Mol. Catal. A: Chem. 135 (1998) 295.
C. R. Jacob, S. P. Varkey and P. Ratnasamy, Appl. Catal. A: Gen. 168 (1998) 353.
C. R. Jacob, S. P. Varkey and P. Ratnasamy, Appl. Catal. A: Gen. 182 (1999) 91.
C. R. Chandra, S. P. Varkey and P. Ratnasamy, Microporous Mesoporous Mater. 22 (1998) 465.
S. Deshpande, D. Srinivas and P. Ratnasamy, J. Catal. 188 (1999) 261.
T. H. Bennur, D. Srinivas and P. Ratnasamy, Microporous Mesoporous Mater. 48 (2001) 111.
T. Joseph, D. Srinivas, C. S. Gopinath and S. B. Halligudi, Catal. Lett. 83 (2002) 209.
R. Robert and P. Ratnasamy, J. Mol. Catal. A: Chem. 100 (1995) 93.
S. A. Chavan, D. Srinivas and P. Ratnasamy, Top. Catal. 11/12 (2000) 359.
S. A. Chavan, D. Srinivas and P. Ratnasamy, J. Catal. 192 (2000) 286.
S. A. Chavan, D. Srinivas and P. Ratnasamy, Chem. Commun. (2001) 1124.
S. A. Chavan, D. Srinivas and P. Ratnasamy, J. Catal. 204 (2001) 409.
W. Partenheimer, Catal. Today 23 (1995) 69.
S. A. Chavan, S. B. Halligudi, D. Srinivas and P. Ratnasamy, J. Mol. Catal. A: Chem. 161 (2000) 49.
S. A. Chavan, D. Srinivas and P. Ratnasamy, J. Catal. 212 (2002) 39.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Srinivas, D., Sivasanker, S. Biomimetic Oxidations Using Transition Metal Complexes Encapsulated in Zeolites. Catalysis Surveys from Asia 7, 121–132 (2003). https://doi.org/10.1023/A:1025381423820
Issue Date:
DOI: https://doi.org/10.1023/A:1025381423820