Synthesis, characterization and electron transfer properties of some picolinate complexes of ruthenium

In aqueous solution ruthenium trichloride reacted with picolinic acid (Hpic) in the presence of a base to afford Ru(pic)₃]. In solution it shows intense ligand-to-metal charge transfer transitions near 310 and 370 nm, together with a low-intensity absorption near 2000 nm. Ru(pic)₃] is one-electron paramagnetic and shows a rhombic ESR spectrum in 1:1 dimethylsulphoxide-methanol solution at 77 K. The distortions from octahedral symmetry have been calculated by ESR data analysis. The axial distortion is larger than the rhombic one. In acetonitrile solution it shows a reversible ruthenium(III)-ruthenium(II) reduction at −0.09 V vs. SCE and a reversible ruthenium(III)-ruthenium(IV) oxidation at 1.52 V vs. SCE. Chemical or electrochemical reduction of Ru^III(pic)₃] gives Ru^II(pic)₃]⁻, which in solution shows intense MLCT transitions near 360, 410 and 490 nm, and is converted back to Ru(pic)₃] by exposure to air. Reaction of Ru(pic)₃] with 8-quinolinol (HQ) in dimethylsulphoxide solution affords RuQ₃]. Ru(bpy)(pic)₂] (bpy = 2,2′-bipyridine) has been prepared by the reaction of Hpic with Ru(bpy)(acac)₂]Cl (acac = acetylacetonate ion) in ethyleneglycol. It is diamagnetic and in solution shows intense MLCT transitions near 370, 410 and 530 nm. In acetonitrile solution it shows a reversible ruthenium(II)-ruthernium(III) oxidation at 0.44 V vs. SCE and a reversible one-electron reduction of bpy at − 1.64V vs. SCE.