A phosphaguanidine [Me2NC(PPh2)=NiPr], the analogous guanidine [Me2NC(NPh2)=NiPr], and their hydrochloride (HCl) salts were prepared to study the influence of substituting a phosphorus atom for a nitrogen atom on the basicity of the two compounds and the bonding in their conjugate acids. The pKa values of both HCl salts were measured in acetonitrile by NMR titration. Surprisingly, the substitution of P for N has essentially no effect on basicity even though the geometry at that atom is changed. The presence of phenyl substituents in the protonated guanidine reduces the resonance in the CN3 core; while poor orbital overlap between P and C reduces the resonance in the N2CP core of the protonated phosphaguanidine. The neutral phosphaguanidine binds to a Cu(I) halide through both the Nimine and the P, which suggested that the basic N atom on the bound ligand may have little utility as a Brønsted base. Fortunately, however, a Cu(I) halide complex of the protonated phosphaguanidine is stable. Thus, the tendency of the basic N to bind to metals does not proscribe it serving as a metal-proximate Brønsted base.