In this work, three novel potent benzimidazolium-derived PEPPSI type palladium complexes, namely dichloro[1-allyl-3-benzylbenzimidazole-2-ylidene]pyridine palladium(II) (1), dichloro[1-allyl-3-(1-naphthylmethyl)benzimidazole-2-ylidene]pyridine palladium(II) (2) and dichloro[1-allyl-3-(9-anthrylmethyl)benzimidazole-2-ylidene]pyridine palladium(II) (3), were synthesized and characterized by single X-ray crystallography, FT-IR and NMR spectroscopy. The results were compared with the relevant calculated data. After structural and spectroscopic determination, the performance of the global reactivity behavior of these derivatives was evaluated by quantum chemical parameters (QCP) obtained from DFT/B3LYP and HF methods utilized with the 6-311 g**/LANL2DZ basis set. Next, NBO analyses were conducted to enlighten the possible interactions that occur for each derivative and this revealed that the main role in the lowering of the stabilization energies of all the derivatives was sourced from n -> pi* and pi -> pi* interactions. Finally, all the complexes were analyzed for their anticancer potential by the molecular docking method with VEGFR (vascular endothelial growth factor receptor), thioredoxin reductase, breast cancer and the dodecamer structure of DNA. (C) 2021 Elsevier Ltd. All rights reserved.