Direct Observation of a Nonheme Iron(IV)鈥揙xo Complex That Mediates Aromatic C鈥揊 Hydroxylation

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• 作者：Sumit Sahu ; Matthew G. Quesne ; Casey G. Davies ; Maximilian D眉rr ; Ivana Ivanovi膰-Burmazovi膰 ; Maxime A. Siegler ; Guy N. L. Jameson ; Sam P. de Visser ; David P. Goldberg
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 1, 2014
• 年：2014
• 卷：136
• 期：39
• 页码：13542-13545
• 全文大小：284K
• ISSN：1520-5126

文摘

The synthesis of a pentadentate ligand with strategically designed fluorinated arene groups in the second coordination sphere of a nonheme iron center is reported. The oxidatively resistant fluorine substituents allow for the trapping and characterization of an Fe^IV(O) complex at 鈭?0 掳C. Upon warming of the Fe^IV(O) complex, an unprecedented arene C鈥揊 hydroxylation reaction occurs. Computational studies support the finding that substrate orientation is a critical factor in the observed reactivity. This work not only gives rare direct evidence for the participation of an Fe^IV(O) species in arene hydroxylation but also provides the first example of a high-valent iron鈥搊xo complex that mediates aromatic C鈥揊 hydroxylation.