化学
甲烷
价(化学)
傅里叶变换离子回旋共振
质谱法
甲烷厌氧氧化
氧气
离子
无机化学
氧化物
分析化学(期刊)
物理化学
有机化学
色谱法
作者
Mingxin Guo,Shaodong Zhou,Xiaoyan Sun
标识
DOI:10.1021/acs.jpclett.2c03786
摘要
Inspired by the activities of P-450 enzyme and Rieske oxygenases in nature, in which the high-valent Fe-oxo complexes play a key role for oxidation of alkanes, the oxidation process of methane by the high-valent iron oxide cation [FeO2]+ has been explored by using Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously reported [FeO]+/CH4 and [Fe(O)OH]+/CH4 systems, which afford [FeOH]+ as the main product, the generation of Fe+ dominates the reaction of [FeO2]+ with CH4. Theoretical calculations suggest a novel "oxygen rebound" pathway for the liberation of methanediol. In particular, the inevitable valence increase of Fe prior to C-H activation is similar to the cytochrome P-450 mediated processes. To our best knowledge, this study provides the first example of methane activation by the high-valent Fe(V)-oxo species in the gas phase, which may thus bridge the gas-phase model and the condensed-phase biosystems.
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