Various catalysts in homogeneous or heterogeneous catalysis deploy unconventional reaction pathways by lowering the activation energy (AE) barrier, controlling the selectivity, and creating environmental impact, thereby bringing about economic viability. Hence, the study of these methodologies is of immense interest. To develop a new chemistry, there is much scope for the invention of brilliant candidates that could effectively catalyze diverse reaction methodologies. The palladium-catalyzed reactions motivate interesting applications on various organic transformations under mild reaction conditions. Although phosphorous designed ligands or catalysts have been used, despite their expensiveness, sensitivity and other properties, there is the necessity of developing even better cross-coupling ligands or catalysts such as N-heterocyclic carbene (NHC)-based palladium complexes. These palladium-NHCs (Pd-NHC) are novel and universal nucleophilic entities that have come into light as the most successful class of catalysts in organometallic chemistry. In the same class, a specific category of palladium-NHCs such as palladium-pyridine enhanced pre-catalyst preparation by the stabilization initiation (palladium-PEPPSI) complexes, are emerging as versatile alternatives to phosphine containing palladium complexes for various cross-coupling reactions due to their excellent catalytic activity. Further to mention that NHCs are recently extensively used as ancillary ligands in organometallic chemistry, which includes industrial-related catalytic transformations due to strong σ-donors to metal centres. Apart from this, many NHC-metal complexes are the fascinating consideration in material science as probable metallo-pharmaceuticals. The current review offers a brief exploration of palladium-PEPPSI complexes over the past few years. Further, the synthesis of a variety of these types of catalysts, their applications in Suzuki-Miyaura, Buchwald-Hartwig, Sonogashira, Negishi couplings direct C2-arylation, O-C(O) cleavage, α-arylation/alkylation of carbonyl compounds and trans-amidation reactions via cross-coupling methodologies, which are covered. Additionally, reported recent developments on reusable heterogeneous PdPEPPSI complexes and their catalytic applications are being covered. Finally, the chiral Pd complexes and their asymmetric transformations are discussed.
C-C/C-heteroatom bond formations; C–H activation; Environmentally sustainable processes; Green synthesis; Heterogeneous catalysis; Homogeneous catalysis; Palladium-NHCs; Palladium-PEPPSI catalysts.