Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions
Irene Prat,Jennifer S. Mathieson,Mireia Güell,Xavi Ribas,Josep M. Luis,Leroy Cronin,Miquel Costas +6 more
TLDR
This study pioneers the implementation of variable-temperature mass spectrometry to investigate reactive intermediates and the generation of a Fe(V)=O species within a synthetic non-haem complex at -40 °C and its reaction with an olefin.Abstract:
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 °C and its reaction with an olefin. Also, with isotopic labelling we were able both to follow oxygen-atom transfer from H(2)O(2)/H(2)O 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.read more
Citations
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High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy
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The biology and chemistry of high-valent iron–oxo and iron–nitrido complexes
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Chemo- and stereoselective CH oxidations and epoxidations/cis-dihydroxylations with H2O2, catalyzed by non-heme iron and manganese complexes
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Ferrates: greener oxidants with multimodal action in water treatment technologies.
TL;DR: Current state-of-the-art applications of Fe(VI) and the associated unique chemistry of these high-valence states of iron are discussed, which will make it possible to unlock the true potential of ferrates for degrading emerging toxins and pollutants, and in the sustainable production and use of nanomaterials in an energy-conserving environment.
References
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