Immobilized metal cluster complexes are of interest as potential catalysts for varied processes. We have elaborated the methods of synthesis of Rh₆- and Os₃-containing monomers and their polymers [1,2]. The cluster-containing polymers were obtained by two ways: i) copolymerization of cluster-containing monomers with traditional monomers such as styrene, acrylonitrile, 4-vinylpyridine, etc.; ii) by polymer-analogous reaction between macroligands and metal carbonyl clusters. The cluster-containing polymers obtained can be considered as precursors of metal nanosized polymer systems with defined dimensions and compositions of the cluster fragments. Heterogenization of the homogeneous catalysts allows one to enhance their activity and to isolate and study the intermediates which are catalytically active. We found that the immobilized metal clusters studied were effective catalysts for hydrogenation and oxidation reactions. Thus, polymer Rh- and Os carbonyl clusters show a high activity in the hydrogenation of cyclohexene or styrene in the repeated cycles. Os₃-containing copolymers were active in the oxidation of cyclohexene by molecular oxygen and oxidative dehydrogenation of 2,3,6-trimethyl hydroquinone. The possible mechanism of these reactions in the presence of polymer-immobilized clusters and the intermediate active species are also discussed.

[1] S.I. Pomogailo, G.I. Dzhardimalieva, A.D. Pomogailo, Macrom. Symp., 2002, 186, 155.
[2] S.I. Pomogailo, G. I. Dzhardimalieva, A.D. Pomogailo. In book "Interfacial Effects and Novel Properties of Nanomaterials", Series "Solid State Phenomena", Trans Tech. Publs., Zürich, 2003, Vol. 94.

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