title: Selective hydrogenation of monosubstituted alkenes by Pd nanoparticles embedded in polyelectrolyte films.
abstract: Pd nanoparticles embedded in multilayer polyelectrolyte films can be easily prepared through layer-by-layer adsorption of poly(acrylic acid) (PAA) and poly(ethyleneimine)-Pd2+ (PEI-Pd(II)) complexes followed by reduction of Pd(II) with NaBH4. Transmission electron microscopy confirms the formation of Pd particles with diameters of 1-3 nm. Remarkably, [PAA/PEI-Pd(0)]3PAA films catalyze the hydrogenation of monosubstituted alkenes with turnover frequencies that are as much as 100-fold higher than turnover frequencies for hydrogenation of multiply substituted double bonds. Selectivities in the hydrogenation of monosubstituted over multisubstituted double bonds are higher than those of Wilkinson's catalyst. Moreover, the turnover frequency for the hydrogenation of allyl alcohol did not change when the catalyst was recycled three times. Intramolecular selectivity for the hydrogenation of monosubstituted alkenes also occurs when substrate molecules contain both mono and multiply substituted double bonds. The combination of the encapsulating polyelectrolyte film and small nanoparticles apparently results in hindered access of multiply substituted double bonds to catalytic sites.
authors.affiliation: Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.
authors.forename: Somnath
authors.initials: S
authors.lastname: Bhattacharjee
authors.forename: Merlin L
authors.initials: ML
authors.lastname: Bruening