Doping Effects in Cluster‐Mediated Bond Activation

Gas-phase investigations of judiciously doped oxide clusters permit to address fundamental challenges related to, for example, the low-temperature oxidation of CO or the selective conversion of hydrocarbons. Modifying the size and composition of a free cluster in a controlled way enables the modification of local charge effects and of spin states, and spectroscopic studies in combination with computational work help to identify the active site of a catalyst and to unravel mechanistic details. Also, the interplay of the support material with the reactive part of a composite catalyst cluster can be addressed. Examples will be presented demonstrating how and why the gas-phase reactivities of heteronuclear clusters, in comparison with their homonuclear counterparts, toward small, generally rather inert molecules can be increased, decreased, or not significantly affected.