Reductive amination can be carried in i-PrOH/H 2 O as hydrogen sources using commercially available iron carbonyl complexes. Inside an aqueous alkaline environment, a hydridocarboferrate is formed and its reducing potential is exploited for hydrogenation of the imine (or iminium ion) in situ obtained from aldehydes or ketones, and primary or secondary amines in almost equimolar ratio. This completely sustainable and hydrogen-free process proceeds at 100 °C using Fe 3 (CO) 12 as catalyst precursor under convectional heating while Fe 2 (CO) 9 gave better results when the reaction was carried out under MW dielectric heating. Either enolizable and not-enolizable aldehydes may be successfully employed in reactions with aliphatic and aromatic amines.