Molecular structure of an Fe(IV) species:.

The molecular structure of the formal iron(IV) porphyrinate derivative, [[Fe(TTP)]2N]SbCl6 (TTP = tetratolylporphyrinate), is reported. The structural parameters are compared to the previously reported species [Fe(TPP)]2N, in which the iron oxidation state is +3.5. Both the equatorial and axial bond distances in [[Fe(TTP)]2N]SbCl6 are slightly shortened and consistent with an increased formal charge on iron. The value for the axial Fe-N distance is 1.6280(7) A, and the average value of the equatorial Fe-Np distances is 1.979(5) A. The Mössbauer isomer shift decreases upon oxidation, again consistent with an increase in formal charge. Values for the isomer shift at room temperature are -0.13 mm/s for [[Fe(TTP)]2N]SbCl6 and 0.04 mm/s for [Fe(TTP)]2N. Crystal data for [[Fe(TTP)]2N]SbCl6 are as follows: orthorhombic, space group Fddd, Z = 8, a = 23.689(2) A, b = 31.056(3) A, c = 22.7788(18) A.