Observation of Fe(v)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions
Observation of Fe(v)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions
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DOI：
10.1038/nchem.1132
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发表时间：
2011-10-01
期刊：
影响因子：
21.8
通讯作者：
Costas, Miquel
中科院分区：
文献类型：
--
作者：
Prat, Irene;Mathieson, Jennifer S.;Costas, Miquel
由铁介导的氧代转移化学是许多生物过程的基础，并且今天在合成上对于难以常规活化的C-H和C=C部分的催化氧化非常重要。尽管在这一领域的大量研究，实验表征的反应性物种在催化条件下是非常有限的，虽然Fe（V）=O部分被假定。在这里，我们显示，使用变温质谱法，在-40摄氏度的合成非血红素复合物内生成Fe（v）=O物种及其与烯烃的反应。此外，与同位素标记，我们能够遵循氧原子从H2 O2/H2O通过Fe（v）=O的产品，并探测作为温度的函数的反应性。本研究开创了变温质谱法研究活性中间体的先河。
Oxo-transfer chemistry mediated by iron underpins many biological processes and today is emerging as synthetically very important for the catalytic oxidation of C-H and C=C moieties that are hard to activate conventionally. Despite the vast amount of research in this area, experimental characterization of the reactive species under catalytic conditions is very limited, although a Fe(v)=O moiety was postulated. Here we show, using variable-temperature mass spectrometry, the generation of a Fe(v)=O species within a synthetic non-haem complex at -40 degrees C and its reaction with an olefin. Also, with isotopic labelling we were able both to follow oxygen-atom transfer from H2O2/H2O through Fe(v)=O to the products and to probe the reactivity as a function of temperature. This study pioneers the implementation of variable-temperature mass spectrometry to investigate reactive intermediates.