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

[Image: see text] 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 (Co(2)P 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 Co(2)P 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 H(2) pressure; these conditions are far milder than previously reported. The air stability and high activity of the Co(2)P 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.