TMEDA in iron-catalyzed Kumada coupling: amine adduct versus homoleptic "ate" complex formation

Robin B Bedford, Peter B Brenner, Emma Carter, Paul M Cogswell, Mairi F Haddow, Jeremy N Harvey, Damien M Murphy, Joshua Nunn, Christopher H Woodall

Research output: Contribution to journalArticle (Academic Journal)peer-review

104 Citations (Scopus)

Abstract

The reactions of iron chlorides with mesityl Grignard reagents and tetramethylethylenediamine (TMEDA) under catalytically relevant conditions tend to yield the homoleptic "ate" complex [Fe(mes)3 ](-) (mes=mesityl) rather than adducts of the diamine, and it is this ate complex that accounts for the catalytic activity. Both [Fe(mes)3 ](-) and the related complex [Fe(Bn)3 ](-) (Bn=benzyl) react faster with representative electrophiles than the equivalent neutral [FeR2 (TMEDA)] complexes. Fe(I) species are observed under catalytically relevant conditions with both benzyl and smaller aryl Grignard reagents. The X-ray structures of [Fe(Bn)3 ](-) and [Fe(Bn)4 ](-) were determined; [Fe(Bn)4 ](-) is the first homoleptic σ-hydrocarbyl Fe(III) complex that has been structurally characterized.

Original languageEnglish
Pages (from-to)1804-1808
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number7
DOIs
Publication statusPublished - 10 Feb 2014

Bibliographical note

Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structured keywords

  • BCS and TECS CDTs

Keywords

  • catalysis
  • cross-coupling
  • Grignard reagents
  • iron
  • ARYL GRIGNARD-REAGENTS
  • ALKYL-HALIDES
  • ORGANIC-SYNTHESIS
  • REACTIVITY
  • COMPOUND
  • STATE

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