Additive and Counterion Effects in Iron-Catalyzed Reactions Relevant to C–C Bond Formation

The use of iron catalysts in carbon-carbon bond forming reactions is of interest as an alternative to precious metal catalysts, offering reduced cost, lower toxicity, and different reactivity. While well-defined ligands such as N -heterocyclic carbenes (NHCs) and phosphines can be highly effective in these reactions, additional additives such as N -methylpyrrolidone (NMP), N,N,N ', N '-tetramethylethylenediamine (TMEDA), and iron salts that alter speciation can also be employed to achieve high product yields. However, in contrast to well-defined iron ligands, the roles of these additives are often ambiguous, and molecular-level insights into how they achieve effective catalysis are not well-defined. Using a unique physical-inorganic in situ spectroscopic approach, detailed insights into the effect of additives on iron speciation, mechanism, and catalysis can inform further reaction development. In this Perspective, recent advances will be discussed as well as ongoing challenges and potential opportunities in iron-catalyzed reactions.