Secondary coordination sphere effects in ruthenium(III) tetraammine complexes: role of the coordinated water molecule.

The complexes trans-[Ru(III)(NH3)4(4-pic)(H2O)](CF3SO3)3 (1) and [Ru(III)(NH3)5(4-pic)](CF3SO3)3 (2) were isolated and studied experimentally by electron paramagnetic resonance (EPR) and UV-vis spectroscopies, cyclic voltammetry, and X-ray crystallography and theoretically by ligand-field theory (LFT) and density functional theory (DFT) calculations. Complex 1 is reported in two different crystal forms, 1a (100 K) and 1b (room temperature). EPR and UV-vis spectroscopies suggest that aqua ligand interaction in this low-spin ruthenium(III) complex changes as a function of hydrogen bonding with solvent molecules. This explicit water solvent effect was explained theoretically by DFT calculations, which demonstrated the effect of rotation of the aqua ligand about the Npic-Ru-Oaq axis. The UV-vis spectrum of 1 shows in an aqueous acid solution a broad- and low-intensity absorption band around 28,500 cm(-1) (ε ≈ 500 M(-1) cm(-1)) that is assigned mainly to a charge-transfer (CT) transition from the equatorial ligands to the Ru ß-4dxy orbital (ß-LUMO) using DFT calculations. The electronic reflectance spectrum of 1 shows a broad and intense absorption band around 25,500 cm(-1) that is assigned to a CT transition from 4-picoline to the Ru ß-4dxz orbital (ß-LUMO) using DFT calculations. The t2g(5) set of orbitals had its energy splitting investigated by LFT. LFT analysis shows that a rhombic component arises from C2v symmetry by a simple π-bonding ligand (H2O in our case) twisting about the trans (C2) axis. This twist was manifested in the EPR spectra, which were recorded for 1 as a function of the solvent in comparison with [Ru(NH3)5(4-pic)](3+) and [Ru(NH3)5(H2O)](3+). Only 1 shows an evident change in the g-tensor values, wherein an increased rhombic component is correlated with a higher nucleophilicity (donor) solvent feature, as parametrized by the Abraham system.