Highly Efficient and Recyclable Au Nanoparticle-Supported Palladium(II) Interphase Catalysts and Microwave-Assisted Alkyne Cyclotrimerization Reactions in Ionic Liquids

The gold nanoparticles with core diameter of 3.9-4.7 nm were stabilized with octanethiolate and dipyridylphosphinicamido undecanethiolate. Without varying the size of central Au cores, palladium complexes were immobilized onto these Au nanoparticles through chelation to the surface-bound dipyridyls. Hybrid catalysts of this type were dissolvable and precipitable, and their structures and reactions were investigated by solution nuclear magnetic resonance (NMR) spectroscopy with a resolution typically attained for soluble systems. These surface-bound Pd(II) complexes were highly effective catalysts for [2+2+2] alkyne cyclotrimerization reactions to give highly congested benzene rings with fairly good selectivity. The catalytic reactivity of these interphase catalysts was even higher than that of their unbound counterparts. In addition, they can be easily separated and quantitatively recovered by simple filtration. The recovered catalysts can be effectively recycled many times and their electron microscopy images and NMR spectra showed negligible difference from those of freshly prepared. The complete transformation by Au-bound Pd(II) catalyst with a loading of 4 mol % can be achieved within 1 h for most alkynes. The same catalysis can be further accelerated in ionic liquid under microwave conditions to give nearly 100% of cyclotrimerized products in minutes.