Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach

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• 作者：Sumit Sahu ; Leland R. Widger ; Matthew G. Quesne ; Sam P. de Visser ; Hirotoshi Matsumura ; Pierre Mo毛nne-Loccoz ; Maxime A. Siegler ; David P. Goldberg
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 24, 2013
• 年：2013
• 卷：135
• 期：29
• 页码：10590-10593
• 全文大小：294K
• 年卷期：v.135,no.29(July 24, 2013)
• ISSN：1520-5126

文摘

The new biomimetic ligands N4Py^2Ph (1) and N4Py^2Ph,amide (2) were synthesized and yield the iron(II) complexes [Fe^II(N4Py^2Ph)(NCCH₃)](BF₄)₂ (3) and [Fe^II(N4Py^2Ph,amide)](BF₄)₂ (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative Fe^IV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin Fe^IIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.