Relatively little attention has been given the coordination chemistry of Pd(II) pincer complexes of form κ³-P,C,P-2-ZPR₂-6-Z'PR₂-phenyl-Pd-X and κ³-P,C,P-2,6-ZPR₂-phenyl-Pd-L⁺ systems for the central-phenyl-to-P linkers Z=O or N(H).  Here we report such research on the synthesis, NMR spectroscopy, and ligand-substitution reactions of the following systems: (i) κ³-P,C,P-4-E-2,6-(OPR₂)₂C₆H₂-Pd (E=F, H; R=Ph, Prⁱ), (ii) κ³-P,C,P-2,6-(N(H)PPrⁱ₂)₂C₆H₃-Pd, (iii) κ³-P,C,P-2-OPPrⁱ₂-6-N(H)PPrⁱ₂-C₆H₃-Pd, and (iv) κ³-N,C,N-4-E-2,6-(CH₂L_N)₂C₆H₂-Pd (L_N = N-pyrazolyl, N-3,5-dimethylpyrazolyl, N-triazolyl). �The most effective route for preparation of both the neutral Pd-X and Pd-L⁺ cations has utilized the respective Pd-MeCN⁺ cations obtained in essentially quantitative yields by stirring Pd-Cl or Pd-I in CDCl₃ with a slight excess of TlPF₆ and five- to tenfold excess of MeCN. These neutral and unipositive species have been characterized by ¹H, ³¹P{¹H}, ¹⁹F, and ¹³C{¹H} NMR spectroscopy.� In addition, ¹H, ³¹P, and ¹⁹F NMR spectroscopy has been used to determine the equilibrium constant values of the ligand-substitution reactions.