The polymer-supported palladium-imidazole complex catalyst was synthesized and characterized by various techniques such as elemental analysis, IR spectroscopy and TG analysis. The physico-chemical properties such as bulk density, surface studies by BET method and swelling studies of catalyst in different solvents were investigated. XPS studies were carried out to identify the oxidation state of palladium in the catalyst. The morphology of the support and the catalyst was studied using scanning electron microscope. Using the synthesized catalyst, hydrogenation of benzylideneaniline and a few of its para substituted derivatives was carried out at ambient conditions. The influence of variation in temperature, concentration of the catalyst as well as the substrate on the rate of reaction was studied. The catalyst showed an excellent recycling efficiency over six cycles without leaching of metal from the polymer support.
a b s t r a c tChloromethylated poly(styrene-divinylbenzene) was modified into coordinating Schiff base bearing ligand which was subsequently complexed with palladium chloride and activated by using sodium borohydride. The polymer-supported palladium complex and activated catalyst were characterized by various techniques such as elemental analysis, X-ray photoelectron spectroscopy, atomic absorption spectroscopy, IR, far IR spectral studies, SEM and thermogravimetric analysis. Surface area measurements by BET method and swelling studies with different solvents for the catalyst were also carried out. Catalytic activity towards hydrogenation of 1-hexene, 1-heptene, 1-octene, cyclohexene, norbornadiene (nbd) and 1,5-cyclooctadiene (1,5-cod) was assessed. The influence of variation in temperature, pressure, concentration of the catalyst as well as the substrate and the nature of the solvent on the rate of the reaction was studied for a few olefins. Recycling ability of the catalyst was also evaluated.
The catalytic activity of a polymer-bound palladium Schiff base catalyst was investigated toward the reduction of aryl nitro compounds under ambient temperature and pressure. The dependence of the rate of hydrogenation of o-nitroaniline and o-nitrotoluene on substrate concentration, catalyst concentration and temperature has been determined. Based on the results obtained a plausible mechanism for the hydrogenation reaction is proposed and a rate expression is deduced. The energy and entropy of activation have been evaluated from the kinetic data. The polymer-bound catalyst was found to be better than its homogeneous analog PdCl 2 (NSBA) [NSBA = N-salicylidene benzylamine] for both stability and reusability. Recycling studies revealed that the catalyst could be used six times without metal leaching or significant loss in activity.
Hydrogenation of various nitroarenes by a polymer-supported palladium-imidazole complex at ambient conditions was investigated. The effect of various substituents upon the rate of hydrogenation of nitrobenzene was studied. The rate of para-substituted nitrobenzene hydrogenation was related to the corresponding Hammett substituent constant. The kinetics of hydrogenation and the reusability of the catalyst were also studied.
Abstract:A polymer-supported palladium-imidazole catalyst was used to catalyze the hydrogenation of various olefins under mild conditions. The rate of hydrogenation was studied. The effects of factors such as substrate concentration, catalyst concentration, partial pressure of hydrogen and temperature on initial rate of reaction of selected olefins were investigated. A mechanism for the reaction was proposed from the rate equation. The effects of the solvent and structure of the olefin on the rate of hydrogenation were investigated. The catalyst showed good reusability without any leaching of metal from the support. The homologous analog of the polymer-supported catalyst could not be used as catalyst for the hydrogenation of olefins in methanol because there was precipitation of the metal during reaction.
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