Elucidating the mode of action of a corrosion inhibitor for iron.

Two polymetallic iron(III) complexes 1 and 2 have been synthesised from the known corrosion inhibitor 3-(4-methylbenzoyl)-propionic acid HL1 and their crystal structures determined. Coordination geometries extracted from these structures have been used as the basis for molecular modelling onto idealised iron(III) oxide surfaces as an aid to understanding the efficacy of inhibitors of the 4-keto acid type. The proposed mode of action involves 1,3-bridging didentate coordination of the carboxylate function of L1 to two FeIII ions, hydrogen-bond formation between the 4-keto group of L1 and a bridging surface hydroxy group, as well as close packing of the aromatic end groups, which should generate a hydrophobic barrier on the surface. Adsorption isotherm experiments have been used to compare the strengths of binding of related carboxylic acids onto iron(III) oxide surfaces and indicate that the presence of the 4-keto function leads to the formation of significantly more stable surface complexes.