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Observation of Fe(V)5O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions

Type: Application

Scientific Paper

Gen. Pharma & Chemistry

Number: Technology

10.1038/NCHEM.1132

OTOF

Year Products

2011

micrOTOF-Q, Cryospray

  Author
 

Irene Prat1†, Jennifer S.Mathieson2†, Mireia Gu¨ell1,3, Xavi Ribas1, Josep M. Luis1,3, Leroy Cronin2* and Miquel Costas1*

  Reference
 

Nature Chemistry Volume: 3, Pages: 788–793 Year published: (2011)

 

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 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.

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