Water-soluble cis-mer-[IrH₂Cl(mtppms)₃] selectively dehydrogenated formic acid with a TOF of 298 000 h⁻¹, a final pressure of 140 bar, and a TON_max of 674 000.

A new synthetic method for obtaining [RhCl(cod)(NHC)] complexes (1–4) (cod = η⁴-1,5-cyclooctadiene, NHC = N-heterocyclic carbene: IMes, SIMes, IPr, and SIPr, respectively) is reported together with the catalytic properties of 1–4 in nitrile hydration. In addition to the characterization of 1–4 in solution by ¹³C NMR spectroscopy, the structures of complexes 3, and 4 have been established also in the solid state with single-crystal X-ray diffraction analysis. The Rh(I)-NHC complexes displayed excellent catalytic activity in hydration of aromatic nitriles (up to TOF = 276 h⁻¹) in water/2-propanol (1/1 v/v) mixtures in air.

The synthesis and characterization of the new Ir(I)-complexes [IrCl(cod)(Bnmim)], [Ir(cod)(emim)(PPh₃)]Cl and [Ir(cod)(Bnmim)(mtppms)] are reported. The zwitterionic complexes [Ir(cod)(NHC)(mtppms)] and Na₂[Ir(cod)(NHC)(mtppts)] (NHC = emim, bmim or Bnmim; mtppms-Na and mtppts-Na₃ = sodium salts of mono- and trisulfonated triphenylphosphine, respectively) were found to be effective precatalysts for transfer hydrogenation of aromatic and aliphatic ketones in basic 2-propanol-water mixtures with initial turnover frequencies up to 510 h⁻¹ at 80 °C, and their catalytic performances were compared to those of [IrCl(cod)(NHC)] complexes (NHC = emim, bmim, Bnmim, IMes) and [Ir(cod)(emim)(PPh₃)]Cl. Three of the catalysts were characterized by single-crystal X-ray diffraction. The reaction rates of the transfer hydrogenation of acetophenone and benzophenone showed strong dependence on the water concentration of the solvent, indicating preferential solvation of the catalytically active metal complexes.