The electronic structure of [Fe(TMP)F2], which is formally a one-electron oxidation equivalent above [FeIII(TMP)F2]−, has been examined in solution by 1H NMR, UV-Vis, and Mössbauer spectroscopy. In CD2Cl2–CD3OD solution at 193 K, the pyrrole-H and m-H signals appeared at 128.2 and 116.7 ppm, respectively. The UV-Vis spectrum showed broad absorption bands at 560–680 nm. The Mössbauer spectrum taken in frozen toluene–methanol solution exhibited a very broad single line from which the IS and QS values were determined by computer simulation to be 0.50 and 0.14 mm s−1, respectively. On the basis of these results, it was concluded that the one-electron oxidized product of [Fe(TMP)F2]− should be formulated as the iron(III) radical cation [FeIII(TMP˙)F2], not as iron(IV) porphyrin [FeIV(TMP)F2] as previously suggested.
You have access to this article
Please wait while we load your content...
Something went wrong. Try again?