Ruthenium carbonyl complexes of 3-(2-(methylthio)phenylazo)-4-hydroxy-3-penten-2-one: Synthesis, spectral characterization, electronic structure and catalytic activity

Graphical abstractRuthenium carbonyl complexes having general formula cis-(CO)-trans-(X)-[Ru(CO)2(HL)X2] (where X = Cl (1) and I (2)) are synthesized and characterized by both experimental and theoretical analysis. The electronic structures of the complexes are explained by quantum mechanical calculations by DFT/B3LYP method. The catalytic activities of the complexes are investigated for the oxidation of primary and secondary alcohols to the respective aldehydes and ketones with moderate to high conversions.Figure optionsDownload full-size imageDownload as PowerPoint slide

The complexes with general formula cis-(CO)-trans-(X)-[Ru(CO)2(HL)X2] (where X = Cl (1) and I (2)) have been synthesized by the reaction of 3-(2-(methylthio) phenylazo)-4-hydroxy-3-penten-2-one (HL) with ruthenium carbonyls, [Ru(CO)2Cl2]n/[Ru(CO)4I2]. The proposed geometry of the complexes has been supported by elemental and mass analysis abetted with several spectroscopic techniques. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 0.88–1.12 V along with ligand based reduction in cyclic voltammetric study. The electronic structure of the complexes has been explained by quantum mechanical calculations by DFT/B3LYP method. Catalytic activities of the compounds are investigated by the oxidation of primary and secondary alcohols to the respective aldehydes and ketones with moderate to high conversions in presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant.