The reaction of a Cp*Ir(III) phosphoramidate complex with secondary amines gives amine, imine-bound Cp*Ir(III) hydride complexes resulting from amine dehydrogenation. These well-characterized species could serve as models of relevant intermediates that have been proposed in catalytic amine dehydrogenation using related N,O-chelated Cp*Ir(III) pyridonate complexes.