Ruthenium(III) complexes with N-(acetyl)-N′-(5-R-salicylidene)hydrazines: Syntheses, structures and properties

The reactions of 1 mol equiv. each of [Ru(PPh3)3Cl2] and N-(acetyl)-N′-(5-R-salicylidene)hydrazines (H2ahsR, R = H, OCH3, Cl, Br and NO2) in alcoholic media afford simultaneously two types of complexes having the general formulae [Ru(HahsR)(PPh3)2Cl2] and [Ru(ahsR)(PPh3)2Cl]. The complexes have been characterized by elemental analysis, magnetic, spectroscopic and electrochemical measurements. Molecular structures of [Ru(HahsH)(PPh3)2Cl2] and [Ru(ahsH)(PPh3)2Cl] have been confirmed by X-ray crystallography. In both species, the PPh3 ligands are trans to each other. The bidentate HahsH− coordinates to the metal ion via the O atom of the deprotonated amide and the imine–N atom in [Ru(HahsH)(PPh3)2Cl2]. In HahsH−, the phenolic OH is involved in a strong intramolecular hydrogen bond with the uncoordinated amide N atom forming a seven-membered ring. In [Ru(ahsH)(PPh3)2Cl], the tridentate ahsH2− binds to the metal ion via the deprotonated amide O, the imine N and the phenolate O atoms. In the electronic spectra, the green [Ru(HahsR)(PPh3)2Cl2] and brown [Ru(ahsR)(PPh3)2Cl] complexes display several absorptions in the ranges 385–283 and 457–269 nm, respectively. Both complexes are low-spin and display rhombic EPR spectra in frozen solutions. Both types of complexes are redox active and display a quasi-reversible ruthenium(III) to ruthenium(II) reduction which is sensitive to the polar effect of the substituent on the chelating ligand. The reduction potentials are in the ranges −0.21 to −0.12 and −0.42 to −0.21 V (versus Ag/AgCl) for [Ru(HahsR)(PPh3)2Cl2] and [Ru(ahsR)(PPh3)2Cl], respectively.

Syntheses, structures and physical properties of two series of ruthenium(III) complexes having the general formulae [Ru(HahsR)(PPh3)2Cl2] and [Ru(ahsR)(PPh3)2Cl] with N-(acetyl)-N′-(5-R-salicylidene)hydrazines (H2ahsR) are described. The rhombic EPR spectra of the complexes are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display a ligand substituent sensitive metal centred reduction.Figure optionsDownload as PowerPoint slide