Kinetic energy barriers that have entirely different origins are the reasons for the impedance of the catalytic N2O/CO redox cycle mediated by both [YAlO2]+. and [Y2O2]+. clusters (see scheme). While oxidation with N2O is the bottleneck for [YAlO2]+., oxidation of [Y2O2]+. with N2O is possible, but reduction of [Y2O3]+. by CO is prevented. This arises because of “doping” effects which can control local charges and spin distributions.