The first five-coordinate, square-pyramidal ruthenium complexes of the general formula [RuCl₂(PPh₃)₂L] have been prepared, where L is a phosphoramidite ligand. The new complexes were employed as catalysts for the amination reactions of propargylic esters (18 h, at room temperature or 45 °C, Cs₂CO₃) to give propargylic amines in isolated yields up to 94%.