Novel iridium(I) complexes bearing N-donor-functionalized N-heterocyclic carbene ligands were synthesized. Although hemilabile coordination of the attached donor is considered beneficial in catalysis, no detailed study of this phenomenon in these systems is available to date. The present report provides insight into the hemilabile bonding properties of a N,N'-bis(pyridin-2-yl)-imidazolylidene (NCN) ligand motif on iridium(I). In most cases, the presented compounds exhibit rare fluxional hemilabile coordination of the N donor, and remarkable performance in catalytic transfer hydrogenation is observed. Further, extensive reactivity studies often led to unexpected products.