N-heterocyclic carbenes (NHCs) represent a leading class of ligands in organometallic chemistry, but have been rarely exploited as stabilizers for metal nanoparticles (NPs). We report the first example of NHC stabilized Pd-NPs that demonstrate long term stability. These NHC Pd-NPs were synthesized by a facile ligand exchange protocol using rationally designed long chained NHCs (LC-NHCs). Furthermore, we demonstrate that the surface modification of Pd-NPs results in significant chemoselectivity in a model reaction.

Herein we describe the synthesis of negatively charged N-heterocyclic carbene (NHC)-functionalized palladium and gold nanoparticles (NPs), which are stable in water for over three months. The formation of these NHC−NPs proceeds via an efficient ligand exchange procedure. This method was successfully applied to different negatively charged NHCs bearing sulfonate and carboxylate groups. The obtained PdNPs were investigated as catalysts in hydrogenation reactions and showed high catalytic activity (TON up to 2500 and TOF up to 2000 h -1 ).

The synthesis of four different bidentate hybrid NHC-thioether ligands is presented. The corresponding palladium nanoparticles are stable in various solvents, depending on the ligand used, and show high chemoselectivity in the hydrogenation of olefins. The solubility of the nanoparticles can be switched multiple times depending on the pH value of the solvent. XPS analysis (which shows a subtle shift in the binding energy) was identified as a convenient tool to establish the binding mode of NHC ligands.

Die Synthese von vier zweizähnigen NHC-Thioether-Hybridliganden wird vorgestellt. Mit diesen Liganden modifizierte Palladium-Nanopartikel sind, in Abhängigkeit des verwendeten Liganden, in verschiedenen Lçsungsmitteln stabil und zeigen eine hohe Chemoselektivität in der Hydrierung von Olefinen. Die Lçslichkeit der Nanopartikel konnte je nachpH-Wert des Lçsungsmittels mehrfachgeschaltet werden. Rçntgen-Photoelektronenspektroskopie (die eine feine Verschiebung in der Bindungsenergie zeigt) wurde als praktische Analysemethode zur Bestimmung des Bindungsmodus des NHC-Liganden identifiziert.

In this article we investigate the effect of multivalency in chiral recognition. To this end, we measured the host-guest interaction of a β-cyclodextrin dimer with divalent chiral guests. We report the synthesis of carbohydrate-based water soluble chiral guests functionalized with two borneol, menthol, or isopinocampheol units in either (+) or (−) configuration. We determined the interaction of these divalent guests with a β-cyclodextrin dimer using isothermal titration calorimetry. It was found that—in spite of a highly unfavorable conformation—the cyclodextrin dimer binds to guest dimers with an increased enantioselectivity, which clearly reflects the effect of multivalency.