A series of water-soluble Ru₂⁵⁺ complexes of the type Ru₂(O₂CCH₃)₃(L)Cl where L = 2,3,4,5,6-F₅ap, 2,4,6-F₃ap, 2-Fap, ap, 2-Meap, 2,6-Me₂ap, or 2,4,6-Me₃ap, where ap is the anilinopyridinate anion, have been characterized as to their structural and physicochemical properties in H₂O and DMSO. Five of the newly synthesized complexes were structurally characterized, and the Ru-Cl bond lengths range from 2.477 to 2.544 Å while the Ru-Ru bond lengths range from 2.2838 to 2.2935 Å. The UV-vis spectra of each compound are characterized by three absorption bands in both H₂O and DMSO, the intensity and position of which vary with both the type of bridging ligand and the solvent. The seven examined Ru₂⁵⁺ complexes exist as 1:1 electrolytes in water, and each undergoes a reversible one-electron reduction assigned to Ru₂⁵⁺/Ru₂⁴⁺ in both investigated solvents. A second irreversible reduction attributed to Ru₂⁴⁺/Ru₂³⁺ is also observed for each compound at more negative potentials in DMSO. A linear free energy relationship exists between the sum of the Hammett substituent constants (Σσ) on the ap-type bridging ligand and the wavenumber of an absorption band for the Ru₂⁵⁺ complexes. A linear relationship is also seen between Σσ and measured E_1/2 values for the Ru₂⁵⁺/Ru₂⁴⁺ process in water containing 0.1 M KCl, but little to no effect is seen between the specific bridging ligand and the structural features of the investigated compounds.

Michelle J. Yates

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