The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures.
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