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A Diiron(III,IV) Imido Species Very Active in Nitrene‐Transfer Reactions
Author(s) -
Gouré Eric,
Avenier Frédéric,
Dubourdeaux Patrick,
Sénèque Olivier,
Albrieux Florian,
Lebrun Colette,
Clémancey Martin,
Maldivi Pascale,
Latour JeanMarc
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201307429
Subject(s) - nitrene , chemistry , catalysis , photochemistry , reactive intermediate , reactivity (psychology) , electrospray ionization , computational chemistry , ion , organic chemistry , medicine , alternative medicine , pathology
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 {Fe III Fe IV NTosyl} 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 Fe IV ion which are likely to confer its high reactivity.