CORRELATION BETWEEN ONE-ELECTRON REDUCTION AND OXYGEN-OXYGEN BOND STRENGTH IN D(O) TRANSITION-METAL PEROXO COMPLEXES

In a series of V(V), Cr(VI), Mo(VI), and W(VI) peroxometal complexes c ontaining different ligands, a correlation has been found between thei r oxygen-oxygen bond strengths, measured by the corresponding vibratio nal frequencies, and their ability to act as one-electron accepters, p rovided by the reduction potentials. The correlation holds for complex es of the same metal containing different ligands as well as for compl exes of the various metals containing the same ligand. The nature of t he ligands in affecting the one-electron-oxidizing ability of the pero xo 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 th e oxygen-oxygen bond is shorter.