The present research work describes the synthesis of five new ligands containing pyridinium amine, [H 2 L 1 ] [OTf] 2 -[H 2 L 5 ][I] 2 from two new precursors, [P 3 Et ][I] and [P 2 Me ][CF 3 SO 3 ]. The structure elucidations of the compounds were confirmed by multinuclear NMR ( 1 H, 13 C), FT-IR and by single crystal XRD techniques. Theoretical DFT studies were carried out to get better insight into the electronic levels and structural features of all the molecules. These synthesized new Pro-PYE ligands [H 2 L 1 ][OTf] 2 -[H 2 L 5 ][I] 2 were found to be significantly active as co-catalysts for Pd(CH 3 CO 2 ) 2 toward Heck-Mizoroki coupling reactions with wide substrate scope in the order