Dramatically Accelerated Selective Oxygen-Atom Transfer by a Nonheme Iron(IV)-Oxo Complex: Tuning of the First and Second Coordination Spheres

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• 作者：Leland R. Widger ; Casey G. Davies ; Tzuhsiung Yang ; Maxime A. Siegler ; Oliver Troeppner ; Guy N. L. Jameson ; Ivana Ivanovi?-Burmazovi? ; David P. Goldberg
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：February 19, 2014
• 年：2014
• 卷：136
• 期：7
• 页码：2699-2702
• 全文大小：305K
• ISSN：1520-5126

文摘

The new ligand N3Py^amideSR and its Fe^II complex [Fe^II(N3Py^amideSR)](BF₄)₂ (1) are described. Reaction of 1 with PhIO at 鈭?0 掳C gives metastable [Fe^IV(O)(N3Py^amideSR)]²⁺ (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe^II(Cl)(N3Py^amideSR)](BF₄)₂ (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe^II(N3Py^amideS(O)R)](BF₄)₂ (4). Catalytic OAT with 1 was also observed.