Switching the Selectivity of Cobalt-Catalyzed Hydrogenation of Nitriles

Previous studies of base metals for catalytic hydrogenation of nitriles to primary amines or secondary aldimines focus on designing complexes with elaborate structures. Herein, we report twin catalytic systems where the selectivity of nitrile hydrogenation can be tuned by including or omitting the ligand HN-((CH2CH2PPr2)-Pr-i)(2) ((PNP)-P-iPr-P-H). Simply treating CoBr2 with NaHBEt3 generates cobalt particles, which can catalyze the hydrogenation of nitriles to primary amines with high selectivity and broad functional group tolerance. Ligating CoBr2 with (PNP)-P-iPr-P-H followed by the addition of NaHBEt3, however, forms a homogeneous catalyst favoring secondary aldimines for both hydrogenation and hydrogenative coupling of benzonitrile.