The alkylation of N-(2-pyridyl)imidazole by the MnI methylene-phosphonium complex [Cp(CO)2Mn(η2-P,C-Ph2P[double bond, length as m-dash]C(H)Ph)]BF4 offers a straightforward route to a tridentate pro-ligand featuring an NHC core and phosphine/pyridine arms. The ability of this PĈN ligand to coordinate in a pincer mode was recognized in RhI, RhIII, and NiII complexes.