With this work, we report the synthesis and full characterization of nickel nanoparticles (NPs) stabilized by N-heterocyclic carbene (NHC) ligands, namely 1,3-bis(cyclohexyl)-1,3-dihydro-2H-imidazol-2-ylidene (ICy) and 1,3-bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IMes). Although the resulting NPs have the same size, they display different magnetic properties and different reactivities, which result from ligand effects. In the context of H/D exchange on pharmaceutically relevant heterocycles, Ni@NHC shows a high chemoselectivity, avoiding the formation of undesired reduced side-products and enabling a variety of H/D exchange on nitrogen-containing aromatic compounds. Using 2-phenylpyridine as a model substrate, it was observed that deuteration occurred preferably at the α position of the nitrogen atom, which is the most accessible position for the C-H activation. In addition, Ni@IMes NPs are also able to fully deuterate the ortho positions of the phenyl substituents.