The triphenolate Robson ligand 2,6-bis{[(2-hydroxyphenyl)imino]methyl}-4-methylphenol (H(3)L) and its alkylated derivatives react with ferric nitrate in the presence of sodium acetate, propionate, or benzoate to yield complexes of the type LFe(2)(O(2)CR)3 (R = C6H5, CH2CH3, CH3). These diferric complexes were characterized by Mossbauer, IR, UV-visible, and H-1 NMR spectroscopies and by cyclic voltammetry. All three benzoates appear to be coordinated to the iron centers in the solid state, and IR spectroscopic evidence indicates that they bridge the two metal centers. Upon dissolution of the complexes in pyridine, one free benzoate ion is observed by C-13 NMR, which suggests that it is displaced from the iron by the pyridine solvent. Varying the carboxylate ligands did not significantly affect the electronic nature of the complex; however, additional alkyl substituents on the macroligand further stabilized the iron(III) metal centers.