A water soluble nanostructured platinum (0) metal catalyst from platinum carbonyl molecular clusters: synthesis, characterization and application in the selective hydrogenations of olefins, ketones and aldehydes

Abstract

High nuclearity platinum carbonyl cluster anions (Chini's clusters) have been used as precursors to prepare a platinum nanocatalyst. The ionic polyelectrolyte poly(diallyldimethylammonium chloride) has been used as the support material for anchoring [Pt₃₀(CO)₆₀]^2- via ion-pairing and subsequent stabilization of the nanoparticles. The polymer-supported material has been studied by spectroscopy (NIR, ¹³C NMR, and IR) and TEM before and after its use as a water soluble hydrogenation catalyst. The nanocatalyst is found to be effective for the chemoselective hydrogenation of olefinic, aldehydic and ketonic double bonds. For most of the substrates isolation of the product and reuse of the catalyst are extremely easy due to the automatic phase separation of the products from the catalyst. The spectral features of the fresh catalyst show retention of the carbonyl ligands and molecular identity of the parent cluster, but after use the carbonyl ligands appear to be lost. TEM of the supported material before and after use as a catalyst shows the presence of platinum nanoparticles with majority (≥70%) of the particles in the range of 2-6 nm. Smaller particles are dominant in the used catalyst and this observation is rationalized on the basis of the known reactivity of Chini's clusters with dihydrogen.