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- Title
A Diiron(III,IV) Imido Species Very Active in Nitrene-Transfer Reactions.
- Authors
Gouré, Eric; Avenier, Frédéric; Dubourdeaux, Patrick; Sénèque, Olivier; Albrieux, Florian; Lebrun, Colette; Clémancey, Martin; Maldivi, Pascale; Latour, Jean ‐ Marc
- Abstract
Metal-catalyzed nitrene transfer reactions arouse intense interest as clean and efficient procedures for amine synthesis. Efficient Rh- and Ru-based catalysts exist but Fe alternatives are actively pursued. However, reactive iron imido species can be very short-lived and getting evidence of their occurrence in efficient nitrene-transfer reactions is an important challenge. We recently reported that a diiron(III,II) complex is a very efficient nitrene-transfer catalyst to various substrates. We describe herein how, by combining desorption electrospray ionization mass spectrometry, quantitative chemical quench experiments, and DFT calculations, we obtained conclusive evidence for the occurrence of an {FeIIIFeIVNTosyl} intermediate that is very active in H-abstraction and nitrene-transfer reactions. DFT calculations revealed a strong radical character of the tosyl nitrogen atom in very low-lying electronic configurations of the FeIV ion which are likely to confer its high reactivity.
- Subjects
IRON ions; IMIDES; CHEMICAL species; NITRENES; CHEMICAL reactions; METAL catalysts; AMINE synthesis
- Publication
Angewandte Chemie, 2014, Vol 126, Issue 6, p1606
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201307429