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

Prat, I., Mathieson, J.S., Güell, M., Ribas, X., Luis, J.M., Cronin, L. and Costas, M. (2011) Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions. Nature Chemistry, 3(10), pp. 788-793. (doi: 10.1038/NCHEM.1132)

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 degrees 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.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Cronin, Professor Lee
• Authors: Prat, I., Mathieson, J.S., Güell, M., Ribas, X., Luis, J.M., Cronin, L., and Costas, M.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Nature Chemistry
• ISSN: 1755-4330
• Published Online: 04 September 2011