A diiron(III,IV) imido species very active in nitrene-transfer reactions

Article abstract of DOI:10.1002/anie.201307429

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^IIIFe^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. Nitrene transfer: An Fe^IIIFe^IV imido intermediate is identified in nitrene-transfer reactions by desorption electrospray ionization mass spectrometry (DESI-MS). DFT calculations show that low-lying Fe^IIIFe^III-^.N-tosyl configurations play a major role in the high reactivity of the intermediate. Copyright