Electronic Configuration of High-Spin Imidazole-Ligated Iron(II) Octaethylporphyrinates

The preparation and characterization of two new five-coordinate, imidazole-ligated, high-spin iron(II) octaethylporphyrinates is described. [Fe(OEP)(1,2-Me2Im)] and [Fe(OEP)(2-MeHIm)] have been characterized by X-ray structure
determinations and temperature-dependent Mössbauer spectroscopy in zero and applied magnetic fields. The
distinction between imidazole-ligated and other ligands in high-spin iron(II) porphyrinates, noted for a series of
tetraarylporphyrinate derivatives (Hu, C.; Roth, A.; Ellison, M. K.; An, J.; Ellis, C. M.; Schiltz, C. E.; Scheidt, W. R.
J. Am. Chem. Soc. 2005, 127, 5675), is seen here as well. The sign of the quadrupole-splitting constant is again
negative, which is unique to the imidazole-ligated derivatives and suggests a distinct electronic structure. The
derivatives again display a remarkable temperature dependence in the quadrupole splitting, which is also seen for
deoxymyoglobin and -hemoglobin. Structural features for the two new derivatives are similar to those seen earlier,
although the core conformations show somewhat more doming character.