Silver(I) and thallium(I) complexes of a diarylamido-based PNP pincer ligand have been prepared and characterized. The silver complex [(PNP)Ag](2) exists as a dimer both in solution and in the solid state and is stable under an ambient atmosphere. Thallium complex (PNP)Tl is, however, monomeric and acutely sensitive to moisture and air. Both reagents serve to transfer PNP into the coordination sphere of divalent nickel, palladium, and platinum. [(PNP)Ag](2) is able to effect PNP transfer in air, but the transfer to nickel(II) is less efficient than that with the thallium(I) analogue.