Ruthenium(II) dichloride complexes of two chiral tetradentate aminosulfoxide ligands, varying only in the N-N linker, were synthesized. With each ligand, two major isomers formed, and these were structurally assigned and characterized through a combination of NMR and UV-vis spectroscopies, X-ray crystallography, and density functional theory calculations. The cis-β geometric isomer was formed by each ligand, whereas the trans and cis-α geometric isomers were significant components for one ligand only. Cyclic voltammetry studies show that only the cis-β isomers undergo linkage isomerism upon oxidation to ruthenium(III), whereas the trans and cis-α isomers show simple reversible redox couples.
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