Dalton Transactions p. 9163 - 9168 (2011)
Update date:2022-08-04
Topics:
Ikezaki, Akira
Takahashi, Masashi
Nakamura, Mikio
The electronic structure of [Fe(TMP)F2], which is formally a one-electron oxidation equivalent above [FeIII(TMP)F 2]-, has been examined in solution by 1H NMR, UV-Vis, and Moessbauer spectroscopy. In CD2Cl2-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 Moessbauer 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.
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