MODELS OF THE CYTOCHROMES - REDOX PROPERTIES AND THERMODYNAMIC STABILITIES OF COMPLEXES OF HINDERED IRON(III) AND IRON(II) TETRAPHENYLPORPHYRINATES WITH SUBSTITUTED PYRIDINES AND IMIDAZOLES

The Fe-III/Fe-II and Fe-II/Fe-I reduction potentials of a series of mo del hemes have been measured by cyclic voltammetry in dimethylformamid e at 25 degrees C as a function of the concentration of added axial li gands. The six porphyrinate ligands utilized were tetraphenylporphyrin (TPP), tetramesitylporphyrin (TMP), and a series of ''hindered'' tetr aphenylporphyrins having substituents (OCH3, F, Cl, Br) on both ortho positions of each of the four phenyl rings. The perchlorato salts of t he iron(III) porphyrinates were utilized for the titrations. The axial ligands utilized were N-methylimidazole, 2-methylimidazole, and pyrid ines of basicities ranging in pK(a)(PyH(+)) from 9.7 to 1.1. From the electrochemical titration, the equilibrium constants (log beta(2) and some log beta(1)) of each iron porphyrinate with each ligand were dete rmined. The values of log beta(2) for the iron(III) complexes decrease in the order Br > Cl > CH3 > OCH3 > H > F, while those for iron(II) d ecrease in the slightly modified order Br > Cl > CH3 > F > OCH3 > H. R ather than electronegativity or electron-donating/withdrawing characte ristics, these results appear to follow primarily the physical size of the ortho substituents: The iron porphyrinates with the largest ortho substituents have the largest equilibrium constants. The hindered (TP P)Fe-II complexes are usually, but not always, more stable than the co rresponding hindered (TPP)Fe-III complexes. For both (TPP)Fe-III and t he hindered (TPP)Fe-III complexes, the slope of the correlation of log beta(2)(III) with the pK(a) of the conjugate acid of the pyridine lig and is 1.0. The equilibrium constants for hindered (TPP)Fe-II complexe s, however, have virtually no dependence upon the base strength of the axial pyridines, while those for (TPP)Fe-II has a slight sensitivity, with a slope of 0.15. In contrast to common belief, 2-methylimidazole readily forms bis complexes with some iron(II) tetraphenylporphyrinat es ((TMP)Fe-II, ((2,6-Cl-2)TPP)Fe-II, and ((2,6-Br-2)(4)(TPP)Fe-II), a lthough it does not with (TPP)Fe-II and its (2,6-F-2)(4)- and (2,6-(OC H3)(2))(4)- counterparts. N-Methylimidazole is unique among the axial ligands of this study, in that the equilibrium constants for binding t o both Fe(III) and Fe(II) are virtually identical for all porphyrinate s studied.