Hydrogenation of nitriles to primary amines catalyzed by an unsupported nanoporous palladium catalyst: understanding the essential reason for the high activity and selectivity of the catalyst.

An efficient and highly selective heterogeneous catalyst system for nitrile hydrogenation was developed using unsupported palladium nanopores (PdNPore). The PdNPore-catalyzed selective hydrogenation of nitriles proceeded smoothly, without any additives, under mild conditions (low H 2 pressure and low temperature) to yield primary amines with satisfactory to excellent yields. Systematic studies demonstrated that the high activity and excellent selectivity of the PdNPore originated from its good Lewis acidity and porous structure. No palladium leached from the PdNPore during the hydrogenation reaction. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A deuterium-hydrogen exchange reaction clearly indicated that the present hydrogenation involves heterolytic H 2 splitting on the surface of the PdNPore catalyst.