Development of Organic Polymer-bound Metal Complex Catalysts
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Preparation of polystyrene and ethylene oligomer-bound transition metal complexes (metal: Pd, Rh, Ni, Ru and Nd) and their catalysis for various organic reactions have been studied. Heterogeneous phosphinated polystyrene-bound Pd(II) complexes prepared by the reaction of phosphinated polystyrene with PdCl2, which could be used for reusable catalysts for selective hydrogenation of olefins and acetylenes, and for codimerization of acetylenes and allylic halides. Cationic Pd(II) complexes obtained from the treatment of the polymeric Pd(II) complexes with AgBF4 had the catalytic activity for selective cooligomerizations of olefins. Reduction of the polymeric Pd(II) complexes with hydrazine gave polymer-bound Pd(0) complexes as stable species, which had catalytic activities for representative types of Pd(0)-induced organic reactions. Aminated polystyrene-bound Rh carbonyl cluster complexes (Rh6, Rh7, and Rh14 species) were selectively formed by the reaction of aminated polystyrenes with Rh6(CO)16 in the presence of H2O and CO. These polystyrene-bound Rh cluster anion complexes catalyzed deoxygenation of various N-O bonds (nitro compounds, oximes, hydroxyl amines, and N-oxides), hydrohydoxymethylation of olefins, and selective reduction of carbonyl compounds under the WGSR conditions. Amino moieties on polystyrene play an important role, both in the generation of active Rh species and the catalysis for the above reactions. Functional linear ethylene oligomers (degrees of polymerization between 150300) having phosphine, phosphinite, and carboxylate ligands were synthesized. The treatment of the functional oligomers with transition metal complexes of Pd, Rh, Ru, Ni, and Nd gave the corresponding oligomer-bound metal complexes, which were recoverable and reusable homogeneous catalysts for a wide variety of organic reactions (hydrogenation, oligomerization, allylic substitution, oxidation, etc.). Such oligomeric complexes dissolved completely in the above reaction conditions at 100110 and cooling the solutions led to quantitative recovery of heterogeneous catalysts. Their reactivity and selectivity in the above reactions accurately mirror those of low molecular weight analogs. A combination catalyst system of ethyleneoligomer-bound Rh(I) complex and polyvinylpyridine-bound Cr(VI) complex could be used for the two-step oxidation reduction sequence (wolf and Lamb reaction); unsaturated alcohols gave directly saturated ketone in a H2 atmosphere. 1993, The Japan Petroleum Institute. All rights reserved.
