Department of Chemistry, School of Medicine, Toho University, Tokyo 143-8540, Japan.
Dalton Trans. 2011 Sep 28;40(36):9163-8. doi: 10.1039/c1dt10561b. Epub 2011 Aug 8.
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 (1)H NMR, UV-Vis, and Mössbauer spectroscopy. In CD(2)Cl(2)-CD(3)OD 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.
通过（1）H NMR、UV-Vis 和 Mössbauer 光谱法，在溶液中研究了[Fe(TMP)F(2)]（形式上是[Fe(III)(TMP)F(2)]-的一个单电子氧化当量以上）的电子结构。在 193 K 的 CD(2)Cl(2)-CD(3)OD 溶液中，吡咯-H 和 m-H 信号分别出现在 128.2 和 116.7 ppm。UV-Vis 光谱显示出 560-680nm 处的宽吸收带。在冷冻的甲苯-甲醇溶液中采集的 Mössbauer 光谱显示出非常宽的单一线，通过计算机模拟确定其 IS 和 QS 值分别为 0.50 和 0.14mm s(-1)。基于这些结果，可以得出结论，[Fe(TMP)F(2)]-的单电子氧化产物应该被表述为铁（III）自由基阳离子[Fe(III)(TMP˙)F(2)]，而不是以前所建议的铁（IV）卟啉[Fe(IV)(TMP)F(2)]。
