Hexahydropyrimidine-based bis(phosphine), a pro-NHC ligand, was synthesized in one step and excellent yield. It underwent spontaneous double C-H bond activation to give cationic pincer NHC complexes of the type [(PCP)MCl]X (M = Pd, Ni and X = Cl, BF4) in the absence of any external reagents. Their structures were determined by X-ray diffraction methods and the mechanism of formation of palladium carbene complexes as analyzed by DFT calculations showed two transition states. The Pd(ii) carbene complex effectively catalyzes a few C-N cross coupling reactions.