Modeling the cis-oxo-labile binding site motif of non-heme iron oxygenases: water exchange and oxidation reactivity of a non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand.
Modeling the cis-oxo-labile binding site motif of non-heme iron oxygenases: water exchange and oxidation reactivity of a non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand.
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DOI：
10.1002/chem.201002297
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发表时间：
2011-02-01
影响因子：
4.3
通讯作者：
Costas, Miquel
中科院分区：
文献类型：
--
作者：
Company, Anna;Prat, Irene;Frisch, Jonathan R.;Mas-Balleste, Ruben;Gueell, Mireia;Juhasz, Gergely;Ribas, Xavi;Muenck, Eckard;Luis, Josep M.;Que, Lawrence, Jr.;Costas, Miquel
描述了一种新合成的非血红素铁(IV)-氧[FeIV(O)(Me,HPytacn)(S)]2+ （2, Me,HPytacn = 1-（2′-吡啶基甲基）-4,7-二甲基-1,4,7-三氮杂环壬烷，S = CH3CN或H2O）的光谱和化学表征。[FeII(CF3SO3)2(Me,HPytacn)](1)与过氧乙酸反应制备了2。配合物2带有一个四齿N4配体，留下两个顺式位点可结合氧基和第二个外部配体，但与四齿配体的相关铁(IV)-氧不同，它在室温下非常稳定（288 K下t1/2 bb0 2h）。通过动力学研究详细分析了它与水交换氧配体氧原子的能力，并在DFT计算的基础上提出了一种机理。研究了碳-氢键的氢原子抽离和2向硫化物的氧原子转移。尽管它的热稳定性，2被证明是一个非常强大的氧化剂，能够破坏环己烷（BDE = 99.3 kcal·mol−1）的强C-H键。
The spectroscopic and chemical characterization of a new synthetic non-heme iron(IV)-oxo species [FeIV(O)(Me,HPytacn)(S)]2+ (2, Me,HPytacn = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, S = CH3CN or H2O) is described. 2 has been prepared by reaction of [FeII(CF3SO3)2(Me,HPytacn)] (1) with peracetic acid. Complex 2 bears a tetradentate N4 ligand that leaves two cis- sites available for binding an oxo group and a second external ligand but, unlike related iron(IV)-oxo of tetradentate ligands, it is remarkably stable at room temperature (t1/2 > 2h at 288 K). Its ability to exchange the oxygen atom of the oxo ligand with water has been analyzed in detail by means of kinetic studies, and a mechanism has been proposed on the basis of DFT calculations. Hydrogen-atom abstraction from C-H bonds and oxygen atom transfer to sulfides by 2 have also been studied. Despite its thermal stability, 2 proves to be a very powerful oxidant that is capable of breaking the strong C-H bond of cyclohexane (BDE = 99.3 kcal·mol−1).
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影响因子：
4.9
作者：
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通讯作者：
Que, L
影响因子：
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作者：
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通讯作者：
Kodanko, Jeremy J.
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通讯作者：
Costas, Miquel
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通讯作者：
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影响因子：
4.3
作者：
Company, Anna;Gomez, Laura;Costas, Miquel
通讯作者：
Costas, Miquel