Correlation between One-Electron Reduction and Oxygen-Oxygen Bond Strength in d0 Transition Metal Peroxo Complexes.

In a series of V(V), Cr(VI), Mo(VI), and W(VI) peroxometal complexes containing different ligands, a correlation has been found between their oxygen-oxygen bond strengths, measured by the corresponding vibrational frequencies, and their ability to act as one-electron accepters, provided by the reduction potentials. The correlation holds for complexes of the same metal containing different ligands as well as for complexes of the various metals containing the same ligand. The nature of the ligands in affecting the one-electron-oxidizing ability of the peroxo complexes appears to play a more important role than the nature of the metal. The correlations found indicate that the electron transfer occurs at less negative potentials for those peroxo complexes where the oxygen-oxygen bond is shorter.