New N‐heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII–NHO complexes have been formed and their use as pre‐catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N‐heterocyclic carbene co‐ligands.