Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: synthesis, characterization and catalytic property.

Mononuclear ruthenium(III) complexes of the type [RuX(EPh(3))(2)(L)] (E=P or As; X=Cl or Br; L=dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX(3)(EPh(3))(3)] (where E=P, X=Cl; E=As, X=Cl or Br) and [RuBr(3)(PPh(3))(2)(CH(3)OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh(3))(2)(DHA-PTSC)] (5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.