The electronic structure of [Fe(TMP)F 2], which is formally a one-electron oxidation equivalent above [Fe III(TMP)F 2] -, has been examined in solution by 1H NMR, UV-Vis, and Mössbauer spectroscopy. In CD 2Cl 2-CD 3OD 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)F 2] - should be formulated as the iron(iii) radical cation [Fe III(TMP) F 2], not as iron(iv) porphyrin [Fe IV(TMP)F 2] as previously suggested.
ASJC Scopus subject areas
- Inorganic Chemistry