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Transition metal complexes bearing an ancillary chelating ligand containing at least one NH functionality are accepted to play a crucial role in metal–ligand bifunctional catalysis originating from M/NH synergetic effects. Substitution of the N–H moiety by an N–Me, or more generally, an N–alkyl group in such systems results in a dramatic drop in catalytic activity, therefore indeed suggesting possible M/NH cooperativity. Herein we report the first M/NH complex (M = Ir), in which N–H/N–Me substitution causes the opposite catalytic effect in the hydrogentation of C=O containing compounds. The origin of this effect will be discussed. Host: Amanda Neukirch |