Abstract
Immobilized Rh6 clusters (cyclohexene hydrogenation catalysts) were prepared by the polymer-analogous transformations or copolymerization of cluster-containing monomers and characterized. Intermediates formed in the course of a catalytic reaction were studied using IR spectroscopy, XPS, and atomic force microscopy. It was found that the relative intensity of a low-energy line in the Rh3d 5/2 spectrum of the initial polymer-immobilized cluster in the XPS spectrum of Rh6 increased in the course of hydrogenation. The catalytic activity of the immobilized complex changed symbatically with both the number of Rh atoms bound to the H(CO) group and the number of Rh atoms, the charge on which was greater than that in the parent cluster. Some experimental evidence was obtained in favor of the hypothesis of cluster fragmentation in the course of hydrogenation with the formation of highly active, most likely, nanosized particles, which are true catalysts, in low concentrations. The surface of macrocomplex particles after hydrogenation became more homogeneous and hydrophilic; this fact is also indicative of an increase in the concentration of polar functional groups in surface layers. This was likely due to Rh-Rh bond cleavage in the polymer-immobilized cluster.
Similar content being viewed by others
References
Pomogailo, A.D., Kinet. Katal., 2004, vol. 45, no. 1, p. 67 [Kinet. Catal. (Engl. Transl.), vol. 45, no. 1, p. 61].
Wohrle, D. and Pomogailo, A.D., Metal Complexes and Metals in Macromolecules, Weinheim: Wiley-VCH, 2003.
Pomogailo, A.D., Catalysis by Polymer-Immobilized Metal Complexes, London: Gordon & Breach, 1998.
Martinengo, S., Chini, P., and Giordano, G., J. Organomet. Chem., 1971, vol. 27, p. 389.
Pomogailo, S.I., Shilov, G.V., Ershova, V.A., Virovets, A.V., Pogrebnyak, V.M., Podberezskaya, N.V., Golovin, A.V., Dzhardimalieva, G.I., and Pomogailo, A.D., J. Organomet. Chem., 2005, vol. 690, p. 4258.
Tekhnologiya katalizatorov (Catalyst Manufacturing Techniques), Mukhlenov, I.P., Ed., Leningrad: Khimiya, 1974.
Povstugar, V.I., Shakov, A.A., Mikhailova, S.S., Voronina, E.V., and Elsukov, E.P., Zh. Anal. Khim., 1998, vol. 53, no. 8, p. 795 [J. Anal. Chem. (Engl. Transl.), vol. 53, no. 8, p. 697].
Magonov, S.N. and Whangbo, M.-H., Surface Analysis with STM and AFM, Weinheim: VCH, 1996.
Pomogailo, A.D., Polimernye immobilizovannye metallokompleksnye katalizatory (Polymer Immobilized Metal Complex Catalysts), Moscow: Nauka, 1988.
Jarrell, M.S., Gates, B.C., and Nicholson, E.D., J. Am. Chem. Soc., 1978, vol. 100, p. 5727.
Rafalko, J.J., Lieto, J., Gates, B., and Schrader, G.L., Chem. Commun., 1978, p. 540.
Dickson, R.S., Homogeneous Catalysis with Compounds of Rhodium and Iridium, Dordrecht: Reidel, 1985.
Pomogailo, S.I., Dzhardimalieva, G.I., Ershova, V.A., Aldoshin, S.M., and Pomogailo, A.D., Macromol. Symp., 2002, vol. 186, p. 155.
Bravaya, N.M., Pomogailo, A.D., Maksakov, V.A., Kirin, V.P., Grachev, V.P., and Kuzaev, A.I., Izv. Akad. Nauk, Ser. Khim., 1995, no. 6, p. 1102.
Fierro, J.L.G., Palacios, J.M., and Tomas, F., Surf. Interface Anal., 1988, vol. 13, p. 25.
Practical Surface Analysis by Auger and X-ray Photoelectron Spectroscopy, Briggs, D. and Seah, M., Eds., Chichester: Wiley, 1983.
Hayden, B.E., King, A., and Newton, M.A., Surf. Sci., 1998, vol. 397, p. 306.
Furlani, C., Mattogno, G., Polzonetti, G., Braca, G., and Valentini, G., Inorg. Chim. Acta, 1983, vol. 69, p. 199.
Carvalho, M., Wieserman, L.F., and Hercules, D.M., Appl. Spectrosc., 1982, vol. 36, p. 290.
Andersson, S.L.T. and Scurrell, M.S., J. Catal., 1979, vol. 59, p. 340.
Pomogailo, S.I., Chuev, I.I., Dzhardimalieva, G.I., Yarmolenko, A.V., Makhaev, V.D., Aldoshin, S.M., and Pomogailo, A.D., Izv. Akad. Nauk. Ser. Khim., 1999, no. 6, p. 1185.
Kholuiskaya, S.N., Pomogailo, A.D., Bravaya, N.M., Pomogailo, S.I., and Maksakov, V.A., Kinet. Katal., 2003, vol. 44, no. 6, p. 831 [Kinet. Catal. (Engl. Transl.), vol. 44, no. 6, p. 761].
Bhaduri, S. and Khwaja, H., J. Chem. Soc., Dalton Trans. 1, 1983, no. 2, p. 419.
Hayden, B.E., King, A., and Newton, M.A., Surf. Sci., 1998, vol. 397, p. 306.
Anderson, S.L.T. and Scurrell, M.S., J. Catal., 1981, vol. 71, p. 233.
Author information
Authors and Affiliations
Additional information
Original Russian Text © S. I. Pomogailo, V.G. Dorokhov, A.M. Lyakhovich, S.S. Mikhailova, G.I. Dzhardimalieva, A.D. Pomogailo, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 5, pp. 742–750.
Synthesis and Reactivity of Metal-Containing Monomers series, report 63.
Rights and permissions
About this article
Cite this article
Pomogailo, S.I., Dorokhov, V.G., Lyakhovich, A.M. et al. Synthesis, structure, and catalytic properties of polymer-immobilized rhodium clusters. Kinet Catal 47, 719–727 (2006). https://doi.org/10.1134/S0023158406050107
Received:
Issue Date:
DOI: https://doi.org/10.1134/S0023158406050107