Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C–H and C=C oxidation reactions
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 characterizat...
| Autores: | , , , , , , |
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| Formato: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2011 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/7147 |
| Acesso em linha: | http://hdl.handle.net/10256/7147 |
| Access Level: | acceso abierto |
| Palavra-chave: | Ferro -- Compostos Iron compounds Catàlisi homogènia Homogeneous catalysis Oxidació Oxidation |
| Resumo: | 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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