Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles
Haitao Tian, Cai‐Yun Ding, Rong‐Zhen Liao, Man Li, Conghui Tang
Abstract
The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such a transformation with high efficiency. A cobalt-centered N, N- bidentate complex was designed and employed as a metal–ligand cooperative dehydrogenation catalyst. Detailed kinetic studies, control experiments, and DFT calculations revealed the crucial hydride transfer, proton transfer, and hydrogen evolution processes. Finally, a tandem outer-sphere/inner-sphere mechanism was proposed for the dehydrogenation of amines to nitriles through an imine intermediate.
Topics & Concepts
DehydrogenationChemistryCobaltCatalysisHydrideImineLigand (biochemistry)DenticityPrimary (astronomy)Transfer hydrogenationCombinatorial chemistryPhotochemistryHydrogenMetalInorganic chemistryOrganic chemistryRutheniumPhysicsBiochemistryAstronomyReceptorAsymmetric Hydrogenation and CatalysisCarbon dioxide utilization in catalysisMetal-Organic Frameworks: Synthesis and Applications