Manganese/ligand association dynamics were studied using a series of structurally related anionic phosphorus ester ligand probes [CH3OP(O)(X)(Y)(-), where X = CH3O, CH3CH2, or H and Y = O, S, or BH3]. Reactions of the probe ions with Mn(H2O)(6)(2+) and a manganese(III) porphyrin ((MnTMPyP5+)-T-III) were studied in aqueous solution by paramagnetic P-31 NMR line-broadening techniques. A satisfactory linear free energy relationship for reactions of the probe ions with Mn(H2O)(6)(2+) and (MnTMPyP5+)-T-III required consideration of both the basicity and solvent affinity of the probe ligands: log(k(app)) = log(k(0)) + α pK(a) + β log(K-ext), where k(0), α, and β are metal complex dependent parameters and pK(a) and K-ext represent the measured Bronsted acidity and water/n-butanol extraction constant for the probe anions, respectively. Reactions of Mn(H2O)(6)(2+) were relatively insensitive to changes in ligand basicity (α = -0.04) and favored the more hydrophilic anions (β = -0.54). These observations are consistent with a dissociative ligand exchange mechanism wherein the outer-sphere complex is stabilized by hydrogen bonding between Mn(H2O)(6)(2+) and the incoming ligand. In contrast, reactions with (MnTMPyP5+)-T-III are accelerated by decreases in both the basicity (α = -0.43) and the hydrophilicity (β = +0.97) of the probe. We conclude that reactions of (MnTMPyP5+)-T-III are also dissociative but that the aromatic groups of the porphyrin provide a hydrophobic environment surrounding the ligand binding site in (MnTMPyP5+)-T-III. Thus, the probe/water solvent interactions must be significantly weakened in order to form the outer-sphere complex that leads to ligand substitution. This work demonstrates the utility of phosphorus relaxation enhancement (PhoRE) techniques for characterizing the second coordination sphere environment of metal complexes leading to ligation and will allow comparison of the second coordination spheres of Mn(H2O)(6)(2+) and (MnTMPyP5+)-T-III to those of other metal complexes.