Dendrimer-Encapsulated Pd Nanoparticles, Immobilized in Silica Pores, as Catalysts for Selective Hydrogenation of Unsaturated Compounds.

Heterogeneous Pd-containing nanocatalysts, based on poly (propylene imine) dendrimers immobilized in silica pores and networks, obtained by co-hydrolysis in situ, have been synthesized and examined in the hydrogenation of various unsaturated compounds. The catalyst activity and selectivity were found to strongly depend on the carrier structure as well as on the substrate electron and geometric features. Thus, mesoporous catalyst, synthesized in presence of both polymeric template and tetraethoxysilane, revealed the maximum activity in the hydrogenation of various styrenes, including bulky and rigid stilbene and its isomers, reaching TOF values of about 230000 h-1. Other mesoporous catalyst, synthesized in the presence of polymeric template, but without addition of Si(OEt)4, provided the trans-cyclooctene formation with the selectivity of 90-95 %, appearing as similar to homogeneous dendrimer-based catalysts. Microporous catalyst, obtained only on the presence of Si(OEt)4, while dendrimer molecules acting as both anchored ligands and template, demonstrated the maximum activity in the hydrogenation of terminal linear alkynes and conjugated dienes, reaching TOF values up to 400000 h-1. Herein the total selectivity on alkene in the case of terminal alkynes and conjugated dienes reached 95-99 % even at hydrogen pressure of 30 atm. The catalysts synthesized can be easily isolated from reaction products and recycled without significant loss of activity.