Catalytic conversions in water: Part 11: Highly active water-soluble palladium-catalysts in the hydrocarboxylation of olefins and the alternating copolymerization of CO and olefins in water

Abstract

Water-soluble palladium complexes of the sodium salt of trisulfonated triphenylphosphine (tppts, P(C 6H 4- m-SO 3Na) 3) catalyze the aqueous biphasic hydrocarboxylation of olefins. High catalytic activities were observed with small, sparingly water-soluble olefins such as propene (TOF>2800 h −1 in the conversion to n- and isobutyric acid). Although selectivities ( n/ iso ratio) were rather moderate in the hydrocarboxylation of propene and 1-octene, high selectivities (>99%) were observed in the conversion of isobutene or cyclopentene to 3-methylbutyric acid and cyclopentanecarboxylic acid, respectively. The water-soluble Pd catalyst based on the bidentate phosphine dpppr-s (1,3-C 3H 6(P(C 6H 4- m-SO 3Na) 2) 2) catalyzes the alternating copolymerization of CO and olefins to polyketones. Activities >4.0 kg of copolymer per gram Pd per hour were found in the alternating copolymerization of CO and ethene.