Two terpolymers of styrene, divinylbenzene, and 1-vinylimidazole (S/DVB/VI) or N-vinylpyrrolidinone (S/DVB/NVP) were prepared by radical polymerization. Palladium nanoparticle catalyst has been "heterogenized" by anchoring to these polymers the [PdCl 2 (PhCN) 2 ] complex via ligand exchange reaction. The formation of coordination bond between S/DVB/VI, S/DVB/NVP terpolymers and Pd 2+ ions was studied using infrared and XPS. Immobilized palladium complex was reduced during hydrogenation reaction or by reaction with sodium borohydride. Characterization of polymer supports and palladium catalysts has involved the measurements of the structural parameters in the dry state by the nitrogen BET adsorption, X-ray photoelectron spectroscopy (XPS), AAS spectroscopy and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Both the catalytic systems were found efficient in the hydrogenation of cinnamaldehyde. The stability and a good recycling efficiency of these catalysts make them useful for prolonged use. The factors influencing selectivity of supported catalysts were discussed. The results offer the possibility of using these terpolymers for the immobilization of metal complex catalysts for hydrogenation and other catalytic reactions.
The hydrosilylation of cyclohexanone and acetone with triethysilane and diphenysilane catalyzed by polymer-supported Rh(I) complex has been investigated. Two terpolymers of styrene, divinylbenzene, and 1-vinylimidazole (S/DVB/VI) or N-vinylpyrrolidinone (S/DVB/ NVP) were used as the catalysts supports. Physical characterization of these materials has involved the measurements of the structural parameters in the dry and swollen states by DSC, the nitrogen BET adsorption method and inverse steric exclusion chromatography ISEC. From these results it can be concluded that the original polymer structure has been changed during the complex attachment giving rise to materials of higher porosity. X-ray photoelectron spectroscopy XPS, IR, and AAS spectroscopy were used to characterization of heterogeneous complexes before and after use. The effect of the morphology of the support on the catalytic properties of the polymersupported Rh(I) species was tested in the hydrosilylation of ketones and correlated with the reaction mechanism. It was demonstrated that the high selectivity of homogeneous rhodium complex toward the silyl ethers can be partially reversed to the dehydrogenative silylation products by a proper choice of polymer support with favorable microporous structure. Recycling tests demonstrated high stability of the supported catalysts during prolonged use. The constant selectivity of the supported catalysts demonstrated during recycling experiments showed that they could be useful for practical application.
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