Synthesis, spectroscopic, magnetic and electrochemical properties of diruthenium-(II,III) and -(III,III) complexes containing the mixed-carboxylato ligand systems CH3CO2––CF3CO2–and C6H5CO2––CF3CO2–

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Abstract
The interaction of the Ru2 5+ tetra-µ-carboxylates [Ru2(O2CR)4Cl](R = CH3 or C6H5) with alcoholic solutions of Ag(O2CCF3) yields the Ru2 5+ mixed-carboxylato, monotrifluoroacetato derivatives [Ru2(O2CR)4(O2CCF3)L2](L = H2O or MeOH). The omission of alcohol and inclusion of trifluoroacetic acid in the reaction medium directs the synthesis to the Ru2 5+ mixed-carboxylato, tris(trifluoroacetato) complexes, [Ru2(O2CR)2(O2CCF3)3(H2O)0.5]. Under aerobic conditions the oxidized, paramagnetic Ru2 6+ tetrakis(trifluoroacetato) complex [Ru2(O2CCH3)2(O2CCF3)4(H2O)2] is obtained. Conductivity measurements, electronic and i.r. absorption spectra, and magnetic susceptibility data are given. Cyclic voltammetry measuements show that increased numbers of CF3CO2 – ligands in the complexes are responsible for an anodic shift in the potential of the Ru2 5+ Ru2 4+ couple. Structures are proposed for the tris- and tetrakis-(trifluoroacetato) complexes.

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