Pincer shaped N-Mesoionic Pyridylidene Amide (PYA) for palladium catalyzed CO2 reduction

•Pd (II) chelated by pincer type mesoionic N-donor pyridylidene amides (PYA) with variation of sterics and electronics.•Detailed structure elucidation of molecular structures of newly synthesized compounds with physical and computational methods.•Pd-PYA as efficient homogeneous electrocatalysts for CO2 reduction with maximum faradaic efficiency of 71 % and minimum overpotential of 0.39 V for CO.•DFT studies of CO2 activation by Pd-PYA. Palladium complexes (4-6) bearing mesoionic N-donor pyridylidene amide ligands (PYAs) with different pendant groups of varying size and electronic properties were successfully synthesized from their respective pro-ligands (1-3). 4-6 were proved effective catalysts for CO2 reduction to synthesis gas. The first principle quantum studies of CO2 reduction provided better insight into the mechanism of these active catalysts. The highest selectivity of 71 % (Faradaic efficiency) and minimum overpotential of 0.390 V was observed for CO. Controlled potential electrolysis (CPE) and post-CPE cyclic voltammogram manifested that all catalysts were robust. [Display omitted]