Renewable polysaccharides as supports for palladium phosphine catalysts

The investigation of the use of polysaccharides derived from natural sources to support metal catalysis has been the focus of several studies. Even though these molecules seem to be attractive materials, their full potential for use in support of heterogeneous catalysis still needs to be revealed. To that end, we developed a new preparation technique for polysaccharide-based palladium catalysts by immobilizing the palladium phosphine complexes on various renewable polysaccharides. The Suzuki cross-coupling in ethanol, using PdCl₂(TPPTS)₂ supported by various polysaccharides, was determined by gas chromatography and compared to homogeneous free-catalyst support. The PdCl₂(TPPTS)₂, that was immobilized on red algae supports, was successfully used as a heterogeneous catalyst in the Suzuki cross-coupling reaction, yielding high activity, higher than that of the homogeneous complex, without leaching. The FTIR spectrometry of representative heterogeneous polysaccharide-based TPPTS-PdCl₂ catalysts was compared to that of native polysaccharide and polysaccharide-based TPP-PdCl₂ catalysts, indicated on new bands, suggesting that the heterogenization occurs via interactions between the sulfonate group on the TPPTS and the hydroxyl groups on the polysaccharides. EDS and XPS analysis were also performed, confirming that the Pd complex was embedded within the i-carrageenan. A comparison of SEM images of i-carrageenan preparations also shed light on the interaction occurring between the polysaccharides and the TPPTS.