Synthesis, structural characterization, electrochemistry and catalytic transfer hydrogenation of ruthenium(II) carbonyl complexes containing tridentate benzoylhydrazone ligands

摘要

Convenient synthesis of eight new octahedral ruthenium(II) carbonyl benzoylhydrazone complexes having the general molecular formula [Ru(L)(CO)(EPh _3) _2](where E = P or As; H _2L = benzoylhydrazone ligand, the two H's representing the two dissociable protons) has been described. The substituted benzoylhydrazone ligands behave as a dianionic tridentate O, N and O donors(L) and coordinates to ruthenium via the phenolate oxygen, the azomethine nitrogen and the deprotonated amide oxygen. The compositions of the complexes have been established by elemental analysis and spectral methods(FT-IR, ~1H NMR, ~(13)C NMR, UV-vis). The crystal structure of one of the complexes, [Ru(L2)(CO)(PPh _3) _2](2), has been solved by single crystal X-ray crystallography and it indicates the presence of a distorted octahedral geometry in these complexes. All the complexes exhibit metal-to-ligand charge transfer(MLCT) transitions in the visible region and display one quasi-reversible reduction and two irreversible oxidations. Further, the catalytic efficiency of the complexes has been investigated in the case of transfer hydrogenation of ketones to the corresponding secondary alcohols. The influence of base, reaction temperature and catalyst loading in transfer hydrogenation reaction was also evaluated. The complexes were found to be efficient catalysts with conversion up to 99.5% in presence of iso-propanol/KOH.