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N,N,N',N'-Tetramethylethylenediamine (TMEDA) has been one of the most prevalent and successful additives used in iron-catalysis, finding application in reactions as diverse as cross-coupling, C-H activation and borylation. However, the role that TMEDA plays in these reactions remains largely undefined. Herein, studying the iron-catalyzed hydromagnesiation of styrene derivatives using TMEDA has provided molecular-level insight into the role of TMEDA in achieving effective catalysis. Key is the initial formation of TMEDA-iron(II) alkyl specie