Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

The reaction of nitrite with ferric and ferrous porphyrins was examined using visible, infrared and NMR spectroscopy. Solutions of either ferric or ferrous porphyrin were stable in the presence of nitrite, with only complexation reactions being observed. Under voltammetric conditions, though, a rapid reaction between nitrite and iron porphyrins was observed to form the nitrosyl complex, Fe(P)(NO), where P=porphyrin. The products of the reduction of ferric porphyrins in the presence of nitrite were confirmed by visible spectroelectrochemistry to be Fe(P)(NO) and [Fe(P)]2O. Visible, NMR and infrared spectroscopy were used to rule out the formation of Fe(P)(NO) by the iron-catalyzed disproportionation of nitrite. A reaction between iron porphyrins and nitrite only occurred by the presence of both oxidation states (ferric/ferrous). The kinetics of the reaction were monitored by visible spectroscopy, and the reaction was found to be first-order with respect to Fe(OEP)(Cl) and Fe(OEP). The products were the same as those observed in the spectroelectrochemical experiment. The rate was not strongly dependent upon the concentration of nitrite, indicating that the coordinated, not the free nitrite, was the reaction species. The kinetics observed were consistent with a mixed oxidation state nitrite-bridged intermediate, which carried out the oxygen transfer reaction from nitrite to the iron porphyrin. The effect of nitrite coordination on the reaction rate was examined. © 2001 Elsevier Science B.V. All rights reserved.