Diruthenium aryl compounds - tuning of electrochemical responses and solubility

Reported herein are the two new series of diruthenium aryl compounds: Ru₂(DiMeOap)₄(Ar) (1a-6a) (DiMeOap = 2-(3,5-dimethoxyanilino)pyridinate) and Ru₂(m-ⁱPrOap)₄(Ar) (1b-5b) (m-ⁱPrOap = 2-(3-iso-propoxyanilino)pyridinate), prepared through the lithium-halogen exchange reaction with a variety of aryl halides (Ar = C₆H₄-4-NMe₂ (1), C₆H₄-4-Bu (2), C₆H₄-4-OMe (3), C₆H₃-3,5-(OMe)₂ (4), C₆H₄-4-CF₃ (5), C₆H₅ (6)). The molecular structures of these compounds were established with X-ray diffraction studies. Additionally, these compounds were characterized using electronic absorption and voltammetric techniques. Compounds 1a-6a and 1b-5b are all in the Ru₂⁵⁺ oxidation state, with a ground state configuration of σ²π⁴δ²(π*δ*)³ (S = 3/2). Use of the modified ap ligands (ap') resulted in moderate increases of product yield when compared to the unsubstituted Ru₂(ap)₄(Ar) (ap = 2-anilinopyridinate) series. Comparisons of the electrochemical properties of 1a-6a and 1b-5b against the Ru₂(ap')Cl starting material reveals the addition of the aryl ligand cathodically shifted the Ru₂^6+/5+ oxidation and Ru₂^5+/4+ reduction potentials. These oxidation and reductions potentials are also strongly dependent on the p-substituent of the axial aryl ligands.