A Mechanistic Analysis of Dehydrogenation Reactions with First-Row Transition Metal Complexes

Over the past decade, the dominance of first-row transition metals in catalytic dehydrogenation reactions has outpaced traditional precious metal-catalyzed processes. This progress has been made possible by the implementation of bifunctional catalysts, where both the metal and ligand actively contribute to the reaction’s outcome. Insights into the behavior of first-row transition metals in catalytic dehydrogenations are being continually upgraded through a combination of experimental and computational studies, thus, greatly advancing our understanding of the underlying reaction mechanisms. In this chapter, we aim to offer a comprehensive perspective on the evolution of rational catalyst design with 3d metals in dehydrogenation reactions, specifically focusing on their preferred mechanistic pathways, thus laying the conceptual groundwork for future developments.