Probing elementary steps of nickel-mediated bond activation in gas-phase reactions: Ligand- and cluster-size effects Review Article

Mass-spectrometry-based experiments, complemented by computational studies, are presented which demonstrate the richness of nickel-containing reagents when employed in various bond-activation processes and conducted under single-collision conditions. We will address the chemistry of “naked” atomic Ni+, the dramatic effects of ligands L or of the size of clusters, which they exhibit in thermal reactions of NiL+ or image (n = 2–30). Special emphasis will be paid to identify elementary steps and to uncover mechanistic principles; as an example, various aspects of the face-selective dehydrogenation of cyclohexane by homo- and heteronuclear cluster-ion dimers are discussed in some detail for the first time.