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

Bedford, Robin B., Brenner, Peter B., Carter, Emma ORCID: https://orcid.org/0000-0001-6691-2377, Cogswell, Paul M., Haddow, Mairi F., Harvey, Jeremy N., Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879, Nunn, Joshua and Woodall, Christopher H. 2014. TMEDA in iron-catalyzed Kumada coupling: amine adduct versus homoleptic "ate" complex formation. Angewandte Chemie International Edition 53 (7) , pp. 1804-1808. 10.1002/anie.201308395

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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. FeI 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 FeIII complex that has been structurally characterized.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Subjects:	Q Science > QD Chemistry
Additional Information:	catalysis; cross-coupling; Grignard reagents; iron
Publisher:	Wiley
ISSN:	1433-7851
Funders:	EPSRC, Pfizer
Last Modified:	12 Dec 2022 09:03
URI:	https://orca.cardiff.ac.uk/id/eprint/58393

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