Modeling TauD-J: A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C-H Bonds
Modeling TauD-J: A High-Spin Nonheme Oxoiron(IV) Complex with High Reactivity toward C-H Bonds
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DOI：
10.1021/ja511757j
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发表时间：
2015-02-25
影响因子：
15
通讯作者：
Que, Lawrence, Jr.
中科院分区：
文献类型：
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作者：
Biswas, Achintesh N.;Puri, Mayank;Que, Lawrence, Jr.
高自旋氧合铁（IV）物种通常涉及非血红素铁加氧酶的机制，它们的C-H键断裂特性归因于五重态自旋。然而，少数可用的合成S = 2 Fe-IV=O配合物支持的多齿配体不裂解强C-H键。本文报道了一种高活性S = 2配合物[Fe-IV（O）（TQA）（NCMe）]（2+）（2）（TQA =三（2-喹啉甲基）胺）的表征，它在-40 ℃下氧化C-H和C-C键。在调节不同的测量温度后，环己烷被2氧化的速率与牛磺酸被TauD-J酶中间体氧化的速率相当。此外，与迄今为止表征的其他S = 2复合物相比，2的光谱性质与TauD-J的光谱性质最相似。这些特征使2成为迄今为止TauD-J的最佳电子和功能模型。
High-spin oxoiron(IV) species are often implicated in the mechanisms of nonheme iron oxygenases, their C-H bond cleaving properties being attributed to the quintet spin state. However, the few available synthetic S = 2 Fe-IV=O complexes supported by polydentate ligands do not cleave strong C-H bonds. Herein we report the characterization of a highly reactive S = 2 complex, [Fe-IV(O)(TQA)(NCMe)](2+) (2) (TQA = tris(2-quinolylmethyl)amine), which oxidizes both C-H and C-C bonds at -40 degrees C. The oxidation of cyclohexane by 2 occurs at a rate comparable to that of the oxidation of taurine by the TauD-J enzyme intermediate after adjustment for the different temperatures of measurement. Moreover, compared with other S = 2 complexes characterized to date, the spectroscopic properties of 2 most closely resemble those of TauD-J. Together these features make 2 the best electronic and functional model for TauD-J to date.