Facilitating the ferration of aromatic substrates through intramolecular sodium mediation

Lewis C. H. Maddock, Manting Mu, Alan R. Kennedy, Max García-Melchor, Eva Hevia

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Abstract

Exploiting cooperative effects between Na and FeII centres present in tris(amide) ferrate complexes has led to the chemoselective ferration of pentafluorobenzene, benzene, toluene, anisole, and pyridine being realised at room temperature. The importance of this bimetallic partnership is demonstrated by neither the relevant sodium amide (NaHMDS or NaTMP) nor the FeII amide Fe(HMDS)2 efficiently metallating these substrates under the conditions of this study. By combining NMR studies with the isolation of key intermediates and DFT calculations, we offer a possible mechanism for how these reactions take place, uncovering a surprising reaction pathway in which the metals cooperate in a synchronised manner. Although the isolated products are formally the result of Fe-H exchange, theoretical calculations indicate that the aromatic substrates undergo Na-H exchange followed by fast intramolecular transmetallation to Fe, thus stabilizing the newly generated aryl fragment.

Original languageEnglish
Pages (from-to)15296-15301
Number of pages6
JournalAngewandte Chemie - International Edition
Volume60
Issue number28
Early online date5 May 2021
DOIs
Publication statusPublished - 5 Jul 2021

Keywords

  • cooperative effects
  • DFT calculations
  • iron
  • metallation
  • sodium

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