Outer-sphere oxidation of the superoxide radical anion

Efforts to use the Marcus model to describe oxidations of the superoxide radical anion (O(2-)) by transition-metal complexes have failed dramatically, with discrepancies between theory and experiment spanning 13 orders of magnitude. As a result, the prevailing view is that these reactions involve some complex interactions that are not yet understood. We now show that once the familiar form of the Marcus cross relation (MCR) is modified to allow for the relatively small size of O(2-), excellent agreement is obtained between theory and experiment. This simple finding dispels the decades of uncertainty surrounding these reactions and provides a reliable method for determining whether oxidations of (O2)- occur via inner- or outer-sphere pathways. More generally, the modified MCR is applicable to any homogeneous electron-transfer process characterized by significant differences in size between electron donors and acceptors.