The synthesis of novel pincer palladium complexes containing ring expanded six-membered N-heterocyclic carbenes (NHCs) via direct metallation of the precursors tetrahydropyrimidin-1-ium hexafluorophosphates in the presence of NaN(SiMe₃)₂ is presented. The structure has been characterized unambiguously by X-ray single crystal analysis. Catalytic activity investigation showed that the complexes catalyzed the Heck reaction of aryl bromides with acrylate/styrene efficiently when using Et₃N as base and DMA as solvent.