Ruthenium‐Catalyzed Dehydrogenation of Primary Amines to Nitriles: Hydrogen Release in Liquid Organic Hydrogen Carriers

The synthesis of new Ru(II) p-cymene complexes of amide-based ligands and their role in hydrogen production and storage via dehydrogenation using amine/nitrile pairs as liquid organic hydrogen carriers (LOHCs) is presented. The substrate scope includes aliphatic (including the long-chain amines) as well as aromatic primary amines. Various biologically important amines were also applicable to this dehydrogenation process, such as furfurylamine, 3-picolylamine, indole-3-methanamine, tryptamine, and 2,6-dichlorobenzylamine. Control experiments, detailed concentration-dependent, and temperature-dependent kinetic studies were carried out, including a Hammett plot. A plausible mechanism for acceptorless double dehydrogenation of primary amines is also proposed on the basis of these analyses, suggesting the presence of Ru-H species. The catalyst's recyclability was tested up to 5 cycles without showing any significant drop in the product yield.