Synthesis and molecular structure of ruthenium(III) benzoylhydrazone complexes: Substituents effect on transfer hydrogenation of ketones

Abstract

An easy and convenient synthesis of a new series of octahedral ruthenium(III) complexes bearing benzoylhydrazone of general formula [Ru(L)Cl(PPh3)2] (where L = 2-hydroxy-1-naphthaldehyde benzoylhydrazone) has been reported. The composition of all the complexes has been unequivocally characterized by microanalysis, IR, electronic, magnetic and EPR spectroscopic techniques. The substituted benzoylhydrazone ligands behave as a dianionic tridentate O, N and O donors and coordinate to ruthenium via the phenolic oxygen, the azomethine nitrogen and the deprotonated amide oxygen. The complexes exhibit moderately strong ligand-to-metal charge transfer transitions in the visible region and intraligand transition in the UV region. Magnetic moment of the complexes (298 K) lies in the range 1.72–1.97 μB reveals the presence of one unpaired electron in the metal centre. The low spin mononuclear Ru(III) benzoylhydrazone complexes display rhombic EPR spectral pattern in frozen solution. The molecular structure of two of the complexes has been established by single crystal X-ray crystallography and indicates the presence of a distorted octahedral geometry in these complexes. Further, the complexes 1–5 have been proven to catalyse the transfer hydrogenation of linear, cyclic and aromatic ketones to their corresponding secondary alcohols in the presence of i-PrOH/KOH at 82 °C and the maximum conversion is up to 99%. The effect of other variables on the transfer hydrogenation reaction such as solvent, base, temperature, time and catalyst loading is also reported.