N-Heterocyclic Carbene (NHC)-Stabilized Ru 0 Nanoparticles: In Situ Generation of an Efficient Transfer Hydrogenation Catalyst

• Published in: Chemistry : a European journal 2020-06, Vol.26 (34), p.7622-7630
• Main Authors: Kathuria, Lakshay, Din Reshi, Noor U, Samuelson, Ashoka G
• Format: Article
• Language: English
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202000142

Tethered and untethered ruthenium half-sandwich complexes were synthesized and characterized spectroscopically. X-ray crystallographic analysis of three untethered and two tethered Ru N-heterocyclic carbene (NHC) complexes were also carried out. These RuNHC complexes catalyze transfer hydrogenation of aromatic ketones in 2-propanol under reflux, optimally in the presence of (25 mol %) KOH. Under these conditions, the formation of 2-3 nm-sized Ru nanoparticles was detected by TEM measurements. A solid-state NMR investigation of the nanoparticles suggested that the NHC ligands were bound to the surface of the Ru nanoparticles (NPs). This base-promoted route to NHC-stabilized ruthenium nanoparticles directly from arene-tethered ruthenium-NHC complexes and from untethered ruthenium-NHC complexes is more convenient than previously known routes to NHC-stabilized Ru nanocatalysts. Similar catalytically active RuNPs were also generated from the reaction of a mixture of [RuCl (p-cymene)] and the NHC precursor with KOH in isopropanol under reflux. The transfer hydrogenation catalyzed by these NHC-stabilized RuNPs possess a high turnover number. The catalytic efficiency was significantly reduced if nanoparticles were exposed to air or allowed to aggregate and precipitate by cooling the reaction mixtures during the reaction.