Abstract
In the oxidation of cyclohexene with H2O2in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H3PMo12-xW x O40(x=0–12), several peroxo species were observed by 31P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM4O8(O2)8]3-(M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H3PMo12-xWxO40. It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
M. Misono, Catal. Rev. 29 (1987) 269; 30 (1988) 339; M.T. Pope and A. Müller, eds., Polyoxometalates: From Platonic Solids to Anti-Retroviral Activity(Kluwer, Dordrecht, 1994) p. 1; C.L. Hill, ed., Polyoxometalates, Chem. Rev. 98 (1998) p. 1.
H. Furukawa, T. Nakamura, H. Inagaki, E. Nishikawa, C. Imai and M. Misono, Chem. Lett. (1988) 877.
K.Y. Lee, K. Itoh, M. Hashimoto, N. Mizuno and M. Misono, in: New Developments in Selective Oxidation II, eds. V. Cortés Corberán and S. Vic Bellón (Elsevier, Amsterdam, 1994) p. 583.
C. Venturello, E. Alneri and M. Ricci, J. Org. Chem. 48 (1983) 3831.
Y. Matoba, H. Inoue, J. Akagi, T. Okabayashi, Y. Ishii and M. Ogawa, Synth. Commun. 14 (1984) 865.
K. Sato, M. Aoki and R. Noyori, Science 281 (1998) 1646.
C. Venturello, R. D'Aloisio, J.C.J. Bart and M. Ricci, J. Mol. Catal. 32 (1985) 107.
C. Aubry, G. Chottard, N. Platzer, J.-M. Brégeault, R. Thouvenot, F. Chauveau, C. Huet and H. Ledon, Inorg. Chem. 30 (1991) 4409.
D.C. Duncan, R.C. Chambers, E. Hecht and C.L. Hill, J. Am. Chem. Soc. 117 (1995) 681.
L. Salles, C. Aubry, R. Thouvenot, F. Robert, C. Dorémieux-Morin, G. Chottard, H. Ledon, Y. Jeannin and J.-M. Brégault, Inorg. Chem. 33 (1994) 871.
L. Salles, C. Aubry, F. Robert, G. Chottard, R. Thouvenot, H. Ledon and J.-M. Brégault, New J. Chem. 17 (1993) 367.
A.C. Dengel, W.P. Griffith and B.C. Parkin, J. Chem. Soc. Dalton Trans. 2683 (1993).
L. Salles, J.-Y. Piquemal, R. Thouvenot, C. Minot and J.-M. Brégeault, J. Mol. Catal. A 117 (1997) 375.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hashimoto, M., Itoh, K., Lee, K.Y. et al. A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids. Topics in Catalysis 15, 265–271 (2001). https://doi.org/10.1023/A:1016600601054
Issue Date:
DOI: https://doi.org/10.1023/A:1016600601054