Novel reactivity of photoexcited iron porphyrins caged into a polyfluoro sulfonated membrane in catalytic hydrocarbon oxygenation

Abstract

Heterogenization of iron porphyrins inside Nafion creates new photocatalytic systems which can be used to oxidize cyclohexene and cyclohexane with sunlight and O₂ under mild conditions (room temperature, atmospheric pressure); the polymeric matrix makes the iron porphyrin a good photocatalyst for the monooxygenation of the substrate and increases both its photocatalytic efficiency (about ten times) and its stability (turnover values >1000).

References

1. (a) K. S. Suslick and R. A. Watson, New. J. Chem., 1992, 16, 633; (b) A. Maldotti, C. Bartocci, G. Varani, A. Molinari, P. Battioni and D. Mansuy, Inorg. Chem., 1996, 35, 1126; (c) L. Weber, R. Hommel, J. Behling, G. Haufe and H. Hennig, J. Am. Chem. Soc., 1994, 116, 2400.
2. E. Polo, R. Amadelli, V. Carassiti and A. Maldotti, Inorg. Chim. Acta, 1992, 192, 1.
3. R. Amadelli, M. Bregola, E. Polo, V. Carassiti and A. Maldotti, J. Chem. Soc., Chem. Commun., 1992, 1355.
4. A. Maldotti, A. Molinari, R. Argazzi, R. Amadelli, P. Battioni and D. Mansuy, J. Mol. Catal., 1996, 114, 141.
5. E. I. Stiefel, in Bioinorganic Catalysis, ed. J. Reedijk, Marcel Dekker, New York, Basel, Hong Kong, 1993, pp. 21–27; L. Barloy, P. Battioni and D. Mansuy, J. Chem. Soc., Chem. Commun., 1990, 1365; J. T. Groves and S. B. Ungashe, J. Am. Chem. Soc., 1990, 112, 7796.
6. Nafion is a Du Pont Nemours registered trademark.
7. Z. Ogumi, T. Kuroe and Z. Takehara, J. Electrochem. Soc., 1985, 132, 2601.
8. C. Bizet, P. Morliere, D. Brault, O. Delgado, M. Bazin and R. Santus, Photochem. Photobiol., 1981, 34, 315; A. Maldotti, C. Bartocci, R. Amadelli and V. Carassiti, J. Chem. Soc., Dalton Trans., 1989, 1197.
9. C. Bartocci, A. Maldotti, G. Varani, P. Battioni, V. Carassiti and D. Mansuy, Inorg. Chem., 1991, 30, 1255.
10. A. Ledwith, P. J. Russel and L. M. Sutcliffe, Proc. R. Soc. London, Ser. A, 1973, 332, 151; A. Maldotti, C. Bartocci, R. Amadelli and V. Carassiti, Inorg. Chim. Acta, 1983, 74, 275.
11. R. Cheng, L. Latos-Grazynsky and A. L. Balch, Inorg. Chem., 1982, 21, 2412.
12. A. Maldotti, C. Bartocci, C. Chiorboli, A. Ferri and V. Carassiti, J. Chem. Soc., Chem. Commun., 1985, 881.
13. A. Maldotti, C. Bartocci, R. Amadelli, G. Varani, E. Polo and V. Carassiti, in Chemistry and Properties of Biomolecular Systems, ed. E. Rizzarelli and T. Theophanides, Kluwer Academic, Dordrecht, Boston, London, 1991.
14. D. N. Hendrickson, M. G. Kinnard and K. S. Suslick, J. Am. Chem. Soc., 1987, 109, 1243.
15. D. Mansuy, Pure Appl. Chem., 1990, 62, 741; B. Meunier, Chem. Rev., 1992, 92, 1411; M. Sono, M. P. Roach, E. D. Coulter and J. H. Dawson, Chem. Rev., 1996, 96, 2841.
16. S. W. Benson, J. Chem. Educ., 1965, 42, 503.