Characterization of a Paramagnetic Mononuclear Nonheme Iron-Superoxo Complex

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• 作者：Chien-Wei Chiang ; Scott T. Kleespies ; Heather D. Stout ; Katlyn K. Meier ; Po-Yi Li ; Emile L. Bominaar ; Lawrence Que ; Jr. ; Eckard M眉nck ; Way-Zen Lee
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：136
• 期：31
• 页码：10846-10849
• 全文大小：268K
• ISSN：1520-5126

文摘

O₂ bubbling into a THF solution of Fe^II(BDPP) (1) at 鈭?0 掳C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and M枚ssbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm^鈥?, which can be assigned to the 谓(O鈥揙) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the Fe^III鈥揙₂^{鈥?/sup> pair found for the O₂ adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that FeIII鈥揙₂鈥?/sup> species can carry out H atom abstraction from a C鈥揌 bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.}