Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex.

Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex.
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DOI:
10.1021/ja504410s
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发表时间:
2014-08-06
影响因子:
15
通讯作者:
Lee, Way-Zen
Lee, Way-Zen
中科院分区:
化学1区
文献类型:
--
作者:
Chiang, Chien-Wei;Kleespies, Scott T.;Stout, Heather D.;Meier, Katlyn K.;Li, Po-Yi;Bominaar, Emile L.;Que, Lawrence, Jr.;Muenck, Eckard;Lee, Way-Zen

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O2 在 -80 °C 下鼓泡进入 FeII(BDPP) (1) 的 THF 溶液中,生成可逆的亮黄色加合物 2。通过共振拉曼光谱和穆斯堡尔光谱进行表征,为了解 2 的性质提供了补充见解。前者在 1125 cm–1 处显示出共振增强振动,可归因于结合超氧化物的 ν(O–O), 而后者揭示了高自旋铁 (III) 中心的存在,该中心与超氧配体交换耦合,如在 4-硝基儿茶酚结合的高原儿茶酸 2,3-双加氧酶的 O2 加合物中发现的 FeIII-O2- 对。最后,2 将二氢蒽氧化为蒽,支持了 FeIII-O2- 物质可以从 C-H 键中提取 H 原子,从而启动某些非血红素铁酶底物的 4 电子氧化的观点。
O2 bubbling into a THF solution of FeII(BDPP) (1) at −80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm–1, which can be assigned to the ν(O–O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the FeIII–O2– pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that FeIII–O2– species can carry out H atom abstraction from a C–H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.
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影响因子: 6.8
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