A TMEDA–Iron Adduct Reaction Manifold in Iron‐Catalyzed C(sp ² )−C(sp ³ ) Cross‐Coupling Reactions

Herein, we expand the current molecular‐level understanding of one of the most important and effective additives in iron‐catalyzed cross‐coupling reactions, N , N , N′ , N′ ‐tetramethylethylenediamine (TMEDA). Focusing on relevant phenyl and ethyl Grignard reagents and slow nucleophile addition protocols commonly used in effective catalytic systems, TMEDA‐iron(II)‐aryl intermediates are identified via in situ spectroscopy, X‐ray crystallography, and detailed reaction studies to be a part of an iron(II)/(III)/(I) reaction cycle where radical recombination with FePhBr(TMEDA) ( 2 Ph ) results in selective product formation in high yield. These results differ from prior studies with mesityl Grignard reagent, where poor product selectivity and low catalytic performance can be attributed to homoleptic iron–ate species. Overall, this study represents a critical advance in how amine additives such as TMEDA can modulate selectivity and reactivity of organoiron species in cross‐coupling.