Ion spectroscopy in methane activation

This review is devoted to ion spectroscopy studies of complexes relevant for the understanding of methane activation with metal ions and clusters. Methane activation starts with the formation of a complex with a metal ion. The degree of the interaction between an intact methane molecule and the ion can be monitored by the perturbations of C–H stretch vibrations in the methane molecule. Binding mediated by the electrostatic interaction results in a η(3) type coordination of methane. In contrast, binding governed by orbital interactions results in a η(2) type coordination of methane. We further review the spectroscopic characterization of activation products of metal–methane reactions, such as the metal–carbene and carbyne products resulting from the interaction of selected 5d metals with methane. The focus of recent research in the field has shifted towards the investigation of interactions between methane and metal clusters. We show examples highlighting that metal clusters can be more reactive in methane activation reactions.