Aminophosphine PNH complexes of Mn(I), Fe(II), and Co(II) and evaluation of their activities in the transfer hydrogenation of nitriles.

A series of Mn(I), Fe(II), and Co(II) complexes with PNH ligands bearing secondary amine functionality were prepared and tested in the catalytic transfer hydrogenation of nitriles using ammonia borane as a hydrogen source. Among all tested complexes, a tetracoordinate Fe(II) bromide, (PNH)FeBr2, proved the most effective, representing a rare example of a highly active iron-based catalytic system for transfer hydrogenation reactions beyond carbonyl compounds and the first example of the iron catalyst for the transfer hydrogenation of nitriles to the corresponding primary amines. Mechanistic studies point out a metal-ligand cooperative mechanism enabled by the secondary amine moiety of the PNH ligand.