Introduction to Homogenous Catalysis with Ruthenium-Catalyzed Oxidation of Alcohols: An Experiment for Undergraduate Advanced Inorganic Chemistry Students

A three-week laboratory experiment, which introduces students in an advanced inorganic chemistry course to air-sensitive chemistry and catalysis, is described. During the first week, the students synthesize RuCl2(PPh3)3. During the second and third weeks, the students characterize the formed coordination compound and use it as a precatalyst for the oxidation of 1-phenylethanol to acetophenone. The synthesized RuCl2(PPh3)3 is characterized using 1H and 31P NMR spectroscopy, IR spectroscopy, and magnetic susceptibility measurements. The students run catalytic and control reactions and determine the percent yield of the product using 1H NMR. The synthesis and catalytic conditions are modified from previously published research articles. The RuCl2(PPh3)3 complex is air sensitive and is prepared under a nitrogen gas atmosphere and worked up in an inert atmosphere glovebox. The catalytic and control reactions are set up in the inert atmosphere glovebox and carried out at reflux outside of the glovebox under a nitrogen gas atmosphere. In this laboratory, the students learn how to set up and run a reaction under a nitrogen atmosphere, how to work in a glovebox, and how to set up and characterize catalytic and control reactions

Hydrogen-transfer catalysis with Cp*Ir^III complexes:The influence of the ancillary ligands

Fourteen Cp*IrIII complexes, bearing various combinations of N- and C-spectator ligands, are assayed in hydrogen-transfer catalysis from isopropyl alcohol to acetophenone under various conditions to investigate ligand effects in this widely used reaction. The new cationic complexes bearing monodentate pyridine and N-heterocyclic carbene (NHC) ligands were characterized crystallographically and by variable-temperature nuclear magnetic resonance (VT-NMR). Control experiments and mercury poisoning tests showed that iridium(0) nanoparticles, although active in the reaction, are not responsible for the high activity observed for the most active precatalyst [Cp*Ir(IMe) 2Cl]BF4 (6). For efficient catalysis, it was found necessary to have both NHCs in monodentate form; tying them together in a bis-NHC chelate ligand gave greatly reduced activity. The kinetics of the base-assisted reaction showed induction periods as well as deactivation processes, and H/D scrambling experiments cast some doubt on the classical monohydride mechanism. © 2013 American Chemical Society

Asymmetric Hydrogen Transfer Reactions Promoted by Homogeneous Transition Metal Catalysts

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