Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds

The development of metal phosphide catalysts for organic synthesis is still in its early stages. Herein, we report the successful synthesis of single-crystal cobalt phosphide nanorods (Co₂P NRs) containing coordinatively unsaturated Co-Co active sites, which serve as a new class of air-stable, highly active, and reusable heterogeneous catalysts for the reductive amination of carbonyl compounds. The Co₂P NR catalyst showed high activity for the transformation of a broad range of carbonyl compounds to their corresponding primary amines using an aqueous ammonia solution or ammonium acetate as a green amination reagent at 1 bar of H₂ pressure; these conditions are far milder than previously reported. The air stability and high activity of the Co₂P NRs is noteworthy, as conventional Co catalysts are air-sensitive (pyrophorous) and show no activity for this transformation under mild conditions. P-alloying is therefore of considerable importance for nanoengineering air-stable and highly active non-noble-metal catalysts for organic synthesis.