We report the reactivity of three binuclear non-heme Fe(III) compounds, namely [Fe-2(bbppnol)(mu-AcO)(H2O)(2)](ClO4)(2) (1), [Fe-2(bbppnol)(mu-AcO)(2)](PF6) (2), and [Fe-2(bbppnol)(mu-OH)(Cl)(2)]center dot 6H(2)O (3), where H(3)bbppnol = N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)-1,3-propanediamine-2-ol, toward the hydrolysis of bis-(2,4-dinitrophenyl)phosphate as models for phosphoesterase activity. The synthesis and characterization of the new complexes 1 and 3 was also described. The reactivity differences observed for these complexes show that the accessibility of the substrate to the reaction site is one of the key steps that determinate the hydrolysis efficiency.